Shelf stable, reduced corrosion, ready to use peroxycarboxylic acid antimicrobial compositions

ABSTRACT

The present invention relates to shelf stable and/or less corrosive peroxycarboxylic acid antimicrobial compositions, including ready-to-use compositions. Shelf stable compositions can include defined ratios of hydrogen peroxide to peroxycarboxylic acid and/or hydrogen peroxide to protonated carboxylic acid, but need not include strong acid. Reduced corrosion compositions can include carboxylic acid and corrosion inhibitor at acid pH. Compositions of the invention can have advantageous activity against spores.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.11/847,604 filed Aug. 30, 2007, and is entitled “Shelf Stable, ReducedCorrosion, Ready to Use Peroxycarboxylic Acid AntimicrobialCompositions”. The entire contents of this patent application is herebyexpressly incorporated herein by reference including, withoutlimitation, the specification, claims, and abstract as well as anyfigures, tables, or drawings thereof.

FIELD OF THE INVENTION

The present invention relates to shelf stable and/or less corrosiveperoxycarboxylic acid antimicrobial compositions, including ready-to-usecompositions. Shelf stable compositions can include defined ratios ofhydrogen peroxide to peroxycarboxylic acid and/or hydrogen peroxide toprotonated carboxylic acid, but need not include strong acid. Reducedcorrosion compositions can include carboxylic acid and corrosioninhibitor at acid pH. Compositions of the invention can haveadvantageous activity against spores.

BACKGROUND OF THE INVENTION

Conventional peroxycarboxylic acid compositions typically include shortchain peroxycarboxylic acids or mixtures of short chain peroxycarboxylicacids and medium chain peroxycarboxylic acids (see, e.g., U.S. Pat. Nos.5,200,189, 5,314,687, 5,409,713, 5,437,868, 5,489,434, 6,674,538,6,010,729, 6,111,963, and 6,514,556). Conventional peroxycarboxyliccompositions including components such as hydrogen peroxide or mineralacid can be corrosive and, at use dilutions, may not have a sufficientlylong shelf life. In addition, some conventional peroxycarboxylic acidcompositions could benefit from increased sporicidal activity.

At neutral and basic pH, corrosion of soft and hard metal surfaces canbe inhibited by mixtures of salts of aliphatic carboxylic acids andtriazole compounds. Such mixtures are used, for example, in engineantifreeze compositions (see, e.g., U.S. Pat. No. 4,647,392). At basicpH, it is believed that the positively charged ion in the salt of thecarboxylic acid is attracted to the electronegative surface of thetarget metal. The aliphatic portion of the carboxylic acid is believedto keep water away from the metal and thus provide a protective coatingagainst corrosion. Such a mechanism cannot explain corrosion protectionat acid pH and these compositions have not previously been showneffective at low pH.

Ongoing research efforts have strived for improved peroxycarboxylic acidcompositions. In particular, these efforts have strived for compositionsthat have increased activity as a sporicide, that have a prolonged shelflife at use dilutions, and/or have reduced corrosiveness.

SUMMARY OF THE INVENTION

The present invention relates to shelf stable and/or less corrosiveperoxycarboxylic acid antimicrobial compositions, including ready-to-usecompositions, which can have advantageous sporicidal activity.

In an embodiment, shelf stable compositions include defined ratios ofhydrogen peroxide to peroxycarboxylic acid and/or hydrogen peroxide toprotonated carboxylic acid, but do not include substantial strong acid.In an embodiment the shelf stable composition includes peroxycarboxylicacid, hydrogen peroxide, and carboxylic acid, but lacks any significantcatalytic or stabilizing concentration of strong acid. The compositioncan include hydrogen peroxide and peroxycarboxylic acid in a ratio ofabout 30:1 to about 60:1. The composition can include hydrogen peroxideand protonated carboxylic acid in a ratio of about 1:1 to about 2:1. Thecomposition can be sufficiently stable that greater than 85% of theinitial concentration of peroxycarboxylic acid remains after 1 year ofstorage at room temperature.

In an embodiment, reduced corrosion compositions include carboxylic acidand corrosion inhibitor at acid pH. In an embodiment the shelf stablecomposition includes peroxycarboxylic acid, hydrogen peroxide, mediumchain mono carboxylic acid or benzoic acid derivative (e.g., benzoicacid or salicylic acid), corrosion inhibitor, and buffer at acid pH.Suitable pH includes about 1 to about 4. In an embodiment, thecomposition corrodes brass at a rate of less than about 250 mil peryear.

The compositions can include short chain peroxycarboxylic acid, mediumchain peroxycarboxylic acid, or a mixture thereof. The compositions canalso include sequestrant, hydrotrope, surfactant, or combinationthereof.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graph showing low corrosion by compositions according to thepresent invention and including a medium chain carboxylic acid and acorrosion inhibitor at acid pH.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, a composition or combination “consisting essentially” ofcertain ingredients refers to a composition including those ingredientsand lacking any ingredient that materially affects the basic and novelcharacteristics of the composition or method. The phrase “consistingessentially of” excludes from the claimed compositions and methods anymineral acid; unless such a mineral acid is specifically listed afterthe phrase.

As used herein, a composition or combination “substantially free of” oneor more ingredients refers to a composition that includes none of thatingredient or that includes only trace or incidental amounts of thatingredient. Trace or incidental amounts can include the amount of theingredient found in another ingredient as an impurity or that isgenerated in a minor side reaction during formation or degradation ofthe peroxycarboxylic acid.

As used herein, the term “strong acid” refers to an acid such a mineralacid such as sulfuric acid, phosphoric acid, nitric acid, andhydrochloric acid; or a strong organic acid such as methane sulfonicacid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid,xylene sulfonic acid, and benzene sulfonic acid. Mineral and otherstrong acids are conventional catalysts for conversion of carboxylicacid to peroxycarboxylic acid. Unsubstituted alkyl carboxylic acids(e.g., short chain and medium chain carboxylic acids) and benzoic acidderivatives (e.g., benzoic acid and salicylic acid) are not strongacids.

As used herein, the term “corrosion” refers to noticeable dissolution ofthe metal, e.g., soft metal, from surfaces or articles which disfigures,modifies or otherwise causes interference with the intendedfunctionality or appearance of the metal.

As used herein, the terms “mixed” or “mixture” when used relating to“peroxycarboxylic acid composition”, “peroxycarboxylic acids”,“percarboxylic acids”, or “carboxylic acids” refer to a composition ormixture including more than one peroxycarboxylic acid or carboxylicacid, such as a composition or mixture including peroxyacetic acid andperoxyoctanoic acid or acetic acid and octanoic acid.

As used herein, the term “microorganism” refers to any noncellular orunicellular (including colonial) organism. Microorganisms include allprokaryotes. Microorganisms include bacteria (including cyanobacteria),lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the term “object” refers to a something material thatcan be perceived by the senses, directly and/or indirectly. Objectsinclude a surface, including a hard surface (such as glass, ceramics,metal, natural and synthetic rock, wood, and polymeric), an elastomer orplastic, woven and non-woven substrates, a food processing surface, ahealth care surface, and the like. Objects also include a food product(and its surfaces); a body or stream of water or a gas (e.g., an airstream); and surfaces and articles employed in hospitality andindustrial sectors. Objects also include the body or part of the body ofa living creature, e.g., a hand.

As used herein, the phrase “food product” includes any food substancethat might require treatment with an antimicrobial agent or compositionand that is edible with or without further preparation. Food productsinclude meat (e.g. red meat and pork), seafood, poultry, fruits andvegetables, eggs, egg products, ready to eat food, grain (e.g., wheat),seeds, roots, tubers, leafs, stems, corms, flowers, nuts, sprouts,seasonings, or a combination or mixture thereof. The term “produce”refers to food products such as fruits and vegetables and plants orplant-derived materials that are typically sold uncooked and, often,unpackaged, and that can sometimes be eaten raw.

As used herein, the phrase “plant product” includes any plant substanceor plant-derived substance that might require treatment with anantimicrobial agent or composition. Plant products include seeds, nuts,nut meats, cut flowers, plants or crops grown or stored in a greenhouse,house plants, and the like. Plant products include many animal feeds.

As used herein, a processed fruit or vegetable refers to a fruit orvegetable that has been cut, chopped, sliced, peeled, ground, milled,irradiated, frozen, cooked (e.g., blanched, pasteurized), orhomogenized. As used herein a fruit or vegetable that has been washed,colored, waxed, hydro-cooled, refrigerated, shelled, or had leaves,stems or husks removed is not processed.

As used herein, the phrase “meat product” refers to all forms of animalflesh, including the carcass, muscle, fat, organs, skin, bones and bodyfluids and like components that form the animal. Animal flesh includesthe flesh of mammals, birds, fishes, reptiles, amphibians, snails,clams, crustaceans, other edible species such as lobster, crab, etc., orother forms of seafood. The forms of animal flesh include, for example,the whole or part of animal flesh, alone or in combination with otheringredients. Typical forms include, for example, processed meats such ascured meats, sectioned and formed products, minced products, finelychopped products, ground meat and products including ground meat, wholeproducts, and the like.

As used herein the term “poultry” refers to all forms of any bird kept,harvested, or domesticated for meat or eggs, and including chicken,turkey, ostrich, game hen, squab, guinea fowl, pheasant, quail, duck,goose, emu, or the like and the eggs of these birds. Poultry includeswhole, sectioned, processed, cooked or raw poultry, and encompasses allforms of poultry flesh, by-products, and side products. The flesh ofpoultry includes muscle, fat, organs, skin, bones and body fluids andlike components that form the animal. Forms of animal flesh include, forexample, the whole or part of animal flesh, alone or in combination withother ingredients. Typical forms include, for example, processed poultrymeat, such as cured poultry meat, sectioned and formed products, mincedproducts, finely chopped products and whole products.

As used herein, the phrase “poultry debris” refers to any debris,residue, material, dirt, offal, poultry part, poultry waste, poultryviscera, poultry organ, fragments or combinations of such materials, andthe like removed from a poultry carcass or portion during processing andthat enters a waste stream.

As used herein, the phrase “food processing surface” refers to a surfaceof a tool, a machine, equipment, a structure, a building, or the likethat is employed as part of a food processing, preparation, or storageactivity. Examples of food processing surfaces include surfaces of foodprocessing or preparation equipment (e.g., slicing, canning, ortransport equipment, including flumes), of food processing wares (e.g.,utensils, dishware, wash ware, and bar glasses), and of floors, walls,or fixtures of structures in which food processing occurs. Foodprocessing surfaces are found and employed in food anti-spoilage aircirculation systems, aseptic packaging sanitizing, food refrigerationand cooler cleaners and sanitizers, ware washing sanitizing, blanchercleaning and sanitizing, food packaging materials, cutting boardadditives, third-sink sanitizing, beverage chillers and warmers, meatchilling or scalding waters, autodish sanitizers, sanitizing gels,cooling towers, food processing antimicrobial garment sprays, andnon-to-low-aqueous food preparation lubricants, oils, and rinseadditives.

As used herein, the phrase “air streams” includes food anti-spoilage aircirculation systems. Air streams also include air streams typicallyencountered in hospital, surgical, infirmity, birthing, mortuary, andclinical diagnosis rooms.

As used herein, the term “waters” includes food process or transportwaters. Food process or transport waters include produce transportwaters (e.g., as found in flumes, pipe transports, cutters, slicers,blanchers, retort systems, washers, and the like), belt sprays for foodtransport lines, boot and hand-wash dip-pans, third-sink rinse waters,and the like. Waters also include domestic and recreational waters suchas pools, spas, recreational flumes and water slides, fountains, and thelike. Waters also include poultry feed waters and waters in dental waterlines.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, facility, or surface therein, or the like that is employed aspart of a health care activity. Health care surfaces include surfaces orequipment in or of an ambulatory care suite or in or of a long term careenvironment. Examples of health care surfaces include surfaces ofmedical or dental instruments, of medical or dental devices, ofelectronic apparatus employed for monitoring patient health, and offloors, walls, or fixtures of structures in which health care occurs.Health care surfaces are found in hospital, surgical, infirmity,birthing, mortuary, and clinical diagnosis rooms. These surfaces can bethose typified as “hard surfaces” (such as walls, floors, bed-pans,etc.,), or fabric surfaces, e.g., knit, woven, and non-woven surfaces(such as surgical garments, draperies, bed linens, bandages, etc.,), orpatient-care equipment (such as respirators, diagnostic equipment,shunts, body scopes, wheel chairs, beds, etc.,), or surgical anddiagnostic equipment. Health care surfaces include articles and surfacesemployed in animal health care. Health care surfaces include dentalwater lines.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning with astabilized composition according to the present invention.

As used herein, the phrases “medical instrument”, “dental instrument”,“dentistry instrument”, “medical device”, “dental device”, “medicalequipment”, or “dental equipment” refer to instruments, devices, tools,appliances, apparatus, and equipment used in medicine or dentistry. Suchinstruments, devices, and equipment can be cold sterilized, soaked orwashed and then heat sterilized, or otherwise benefit from cleaning in acomposition of the present invention. These various instruments, devicesand equipment include, but are not limited to: diagnostic instruments,trays, pans, holders, racks, forceps, scissors, shears, saws (e.g. bonesaws and their blades), hemostats, knives, chisels, rongeurs, files,nippers, drills, drill bits, rasps, burrs, spreaders, breakers,elevators, clamps, needle holders, carriers, clips, hooks, gouges,curettes, retractors, straightener, punches, extractors, scoops,keratomes, spatulas, expressors, trocars, dilators, cages, glassware,tubing, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes,stethoscopes, and arthoscopes) and related equipment, and the like, orcombinations thereof.

As used herein, “agricultural” or “veterinary” objects or surfacesinclude animal feeds, animal watering stations and enclosures, animalquarters, animal veterinarian clinics (e.g. surgical or treatmentareas), animal surgical areas, and the like.

As used herein, “residential” or “institutional” objects or surfacesinclude those found in structures inhabited by humans and encountered ingeneral housekeeping. Such objects or surfaces include bathroom surfaces(e.g., fixture, floor and wall); lavatory surfaces (e.g., fixture, floorand wall), drains, drain surfaces, kitchen surfaces, and the like.

As used herein, weight percent (wt-%), percent by weight, % by weight,and the like are synonyms that refer to the concentration of a substanceas the weight of that substance divided by the weight of the compositionand multiplied by 100. Unless otherwise specified, the quantity of aningredient refers to the quantity of active ingredient.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions of the invention or employed in the methods of theinvention refers to variation in the numerical quantity that can occur,for example, through typical measuring and liquid handling proceduresused for making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. The term about alsoencompasses amounts that differ due to different equilibrium conditionsfor a composition resulting from a particular initial mixture. Whetheror not modified by the term “about”, the claims include equivalents tothe quantities.

For the purpose of this patent application, successful microbialreduction is achieved when the microbial populations are reduced by atleast about 90%, or by significantly more than is achieved by a flushwith water. Larger reductions in microbial population provide greaterlevels of protection.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25±2° C., against several test organisms.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2).

As used herein, the term “sterilant” refers to an agent that destroysall viable forms of microbial life.

As used in this invention, the term “sporicide” refers to a physical orchemical agent or process having the ability to cause greater than a 90%reduction (1-log order reduction) in the population of spores ofBacillus subtilis, Colstridium difficile, or Clostridium sporogeneswithin 30 min at room temperature. In certain embodiments, thesporicidal compositions of the invention provide greater than a 99%reduction (2-log order reduction), greater than a 99.99% reduction(4-log order reduction), greater than a 99.999% reduction (5-log orderreduction) in such population, or total inactivation of endosporeswithin 30 min at room temperature. In an embodiment, the presentsporicidal composition eliminates all bacterial endospores within thestated time and temperature, e.g., 30 min at room temperature. Such atest can start with at least 10⁴ spores on each carrier suture.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can effect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, biostatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor orbiostatic composition.

The Present Compositions

The present invention relates to peroxycarboxylic acid antimicrobialcompositions, including ready-to-use compositions, which haveadvantageous sporicidal activity, advantageous stability, and/oradvantageously reduced corrosiveness. In an embodiment, the presentcompositions unexpectedly have increased and more rapid activity againstspores (e.g., bacterial or fungal spores) and/or viruses at roomtemperature. For example, embodiments of the present compositions haveadvantageous sporicidal activity against Clostridium difficile anddifficult to kill bacterial endospores, such as those of Clostridiumsporogenes and Bacillus subtilis. Further, the present compositions arealso active against vegetative bacteria, vegetative fungi, otherbacterial spores, fungal spores, and viruses. Labels of conventionalsporicidal products state that they require 5 to 32 hours to kill sporesat room temperature (i.e., ambient conditions). At least one embodimentof the present invention kills spores to the same level in only 30minutes. This is surprisingly and advantageously only 1/10^(th) to1/64^(th) of the time required by conventional products.

In an embodiment, the present compositions are unexpectedly lesscorrosive than conventional peroxycarboxylic acid compositions.Conventional corrosion inhibitors (e.g., triazole and fatty acid) areknown to work at basic pH and the conventionally described mechanism ofaction requires basic pH. Applicants have unexpectedly discovered that,at acid pH, a mixture of medium chain mono carboxylic acid or benzoicacid derivative and corrosion inhibitor reduces corrosion compared to acomposition lacking such a carboxylic acid and/or the corrosioninhibitor. In certain embodiments, the composition has pH of about 1 toabout 5, about 1 to about 4.5, or about 1 to about 4 and includes mediumchain mono carboxylic acid or benzoic acid derivative and corrosioninhibitor (e.g., triazole corrosion inhibitor). The present compositionscan provide, at an acid pH, reduced corrosion of, for example, softmetals, such as mild steel, aluminum, or brass. In an embodiment thepresent composition corrodes brass at a rate of less than about 250 milper year. In an embodiment the present composition corrodes brass at arate of less than about 100 mil per year.

In an embodiment, the present compositions unexpectedly have increasedstorage stability, which allows the compositions to retain antimicrobialactivity for longer times after they are made. Surprisingly, the presentcompositions retain high levels of peroxycarboxylic acid in the absenceof significant levels of strong acid (e.g., sulfuric acid). In anembodiment, the present compositions do not include substantial strongacid. Although not limiting to the present invention, the storagestability of the present compositions is believed to result from theratio of hydrogen peroxide to peroxycarboxylic acid and/or the ratio ofhydrogen peroxide to protonated carboxylic acid. For example, the ratioof hydrogen peroxide to peroxycarboxylic acid can be about 30:1 to about60:1. For example, the ratio of hydrogen peroxide to protonatedcarboxylic acid can be about 1:1 to about 2:1.

In certain embodiments, the composition includes a defined ratio ofhydrogen peroxide to peroxycarboxylic acid, a defined ratio of hydrogenperoxide to protonated carboxylic acid, or a defined ratio of hydrogenperoxide to peroxycarboxylic acid and of hydrogen peroxide to protonatedcarboxylic acid. It is believed that the defined ratio is effective toprovide prolonged shelf life to the compositions of the presentinvention. For example, the defined ratio or ratios can provide acomposition of the invention that is storage stable for at least 1 monthat 40° C., for 12 months at typical room temperatures (20-25° C.), oreven longer at room temperature.

A storage stable composition, at the predetermined time limit, stillcontains an antimicrobially effective concentration of peroxycarboxylicacid. In certain embodiments, for example, at the predetermined timelimit, a storage stable composition can have more than 75% of theinitial concentration of peroxycarboxylic acid, more than 80% of theinitial concentration of peroxycarboxylic acid, more than 85% of theinitial concentration of peroxycarboxylic acid, more than 90% of theinitial concentration of peroxycarboxylic acid, or more than 95% of theinitial concentration of peroxycarboxylic acid. In an embodiment, at thepredetermined time limit, a storage stable composition of the presentinvention has more than 85% of the initial concentration ofperoxycarboxylic acid.

In certain embodiments, for example, at the predetermined time limit, astorage stable composition can have more than 80% of the initialconcentration of medium chain carboxylic acid, more than 85% of theinitial concentration of medium chain carboxylic acid, more than 90% ofthe initial concentration of medium chain carboxylic acid, or more than95% of the initial concentration of medium chain peroxycarboxylic acid.In an embodiment, at the predetermined time limit, a storage stablecomposition of the present invention has more than 85% of the initialconcentration of medium chain peroxycarboxylic acid.

In certain embodiments, for example, at the predetermined time limit, astorage stable composition can have more than 80% of the initialconcentration of hydrogen peroxide, more than 85% of the initialconcentration of hydrogen peroxide, more than 90% of the initialconcentration of hydrogen peroxide, or more than 95% of the initialconcentration of hydrogen peroxide. In an embodiment, at thepredetermined time limit, a storage stable composition of the presentinvention has more than 85% of the initial concentration of hydrogenperoxide.

In an embodiment, at the predetermined time limit, the storage stablecomposition can have more than 80% of the initial concentration ofperoxycarboxylic acid, more than 85% of the initial concentration ofmedium chain carboxylic acid, and more than 85% of the initialconcentration of hydrogen peroxide. In an embodiment, at thepredetermined time limit, the storage stable composition can have morethan 85% of the initial concentration of peroxycarboxylic acid, morethan 90% of the initial concentration of medium chain carboxylic acid,and more than 90% of the initial concentration of hydrogen peroxide.

In certain embodiments, the composition includes a defined ratio ofhydrogen peroxide to peroxycarboxylic acid. In certain embodiments, theratio of hydrogen peroxide to peroxycarboxylic acid is less than about1000:1, about 5:1 to about 1000:1, about 13:1 to about 800:1, or about16:1 to about 400:1. In certain embodiments, the ratio of hydrogenperoxide to peroxycarboxylic acid is about 10:1 to about 200:1, about25:1 to about 100:1, about 30:1 to about 60:1, or about 50:1. These canbe weight ratios or ratios of concentration, such as ppm. Thecomposition can include any of these ratios or amounts not modified byabout. In an embodiment, the compositions do not include a substantialamount of strong acid. In an embodiment, the compositions do not includea substantial amount of mineral acid.

In certain embodiments, the composition includes a defined ratio ofhydrogen peroxide to protonated carboxylic acid. In certain embodiments,the ratio of hydrogen peroxide to protonated carboxylic acid is lessthan about 10:1, about 1:5 to about 10:1, about 0.5:1 to about 8:1,about 1:1 to about 8:1. In certain embodiments, the ratio of hydrogenperoxide to protonated carboxylic acid about 0.2:1 to about 10:1, about0.5:1 to about 4:1, about 1:1 to about 2:1, or about 1.4:1. Thecomposition can include any of these ratios or amounts not modified byabout. These can be weight ratios or ratios of concentration, such asppm. In an embodiment, the compositions do not include a substantialamount of strong acid. In an embodiment, the compositions do not includea substantial amount of mineral acid.

In certain embodiments, the composition includes a defined ratio ofhydrogen peroxide to peroxycarboxylic acid and of hydrogen peroxide toprotonated carboxylic acid. In certain embodiments, the ratio ofhydrogen peroxide to peroxycarboxylic acid is about 10:1 to about 200:1and the ratio of hydrogen peroxide to protonated carboxylic acid isabout 0.2:1 to about 10:1, about 0.5:1 to about 4:1, about 1:1 to about2:1, or about 1.4:1. In certain embodiments, the ratio of hydrogenperoxide to peroxycarboxylic acid is about 25:1 to about 100:1 and theratio of hydrogen peroxide to protonated carboxylic acid is about 0.2:1to about 10:1, about 0.5:1 to about 4:1, about 1:1 to about 2:1, orabout 1.4:1.

In certain embodiments, the ratio of hydrogen peroxide toperoxycarboxylic acid is about 30:1 to about 60:1 and the ratio ofhydrogen peroxide to protonated carboxylic acid is about 0.2:1 to about10:1, about 0.5:1 to about 4:1, about 1:1 to about 2:1, or about 1.4:1.In certain embodiments, the ratio of hydrogen peroxide toperoxycarboxylic acid is about 50:1 and the ratio of hydrogen peroxideto protonated carboxylic acid is about 0.2:1 to about 10:1, about 0.5:1to about 4:1, about 1:1 to about 2:1, or about 1.4:1. The compositioncan include any of these ratios or amounts not modified by about. Thesecan be weight ratios or ratios of concentration, such as ppm. In anembodiment, the compositions do not include a substantial amount ofstrong acid. In an embodiment, the compositions do not include asubstantial amount of mineral acid.

In certain embodiments, the ratio of hydrogen peroxide to protonatedcarboxylic acid is about 0.2:1 to about 10:1 and the ratio of hydrogenperoxide to peroxycarboxylic acid is about 10:1 to about 200:1, about25:1 to about 100:1, about 30:1 to about 60:1, or about 50:1. In certainembodiments, the ratio of hydrogen peroxide to protonated carboxylicacid is about 0.5:1 to about 4:1 and the ratio of hydrogen peroxide toperoxycarboxylic acid is about 10:1 to about 200:1, about 25:1 to about100:1, about 30:1 to about 60:1, or about 50:1. In certain embodiments,the ratio of hydrogen peroxide to protonated carboxylic acid is about1:1 to about 2:1 and the ratio of hydrogen peroxide to peroxycarboxylicacid is about 10:1 to about 200:1, about 25:1 to about 100:1, about 30:1to about 60:1, or about 50:1. In certain embodiments, the ratio ofhydrogen peroxide to protonated carboxylic acid is about 1.4:1 and theratio of hydrogen peroxide to peroxycarboxylic acid is about 10:1 toabout 200:1, about 25:1 to about 100:1, about 30:1 to about 60:1, orabout 50:1. In certain embodiments, the ratio of hydrogen peroxide toprotonated carboxylic acid is less than about 1.2:1 and the ratio ofhydrogen peroxide to peroxycarboxylic acid is about 10:1 to about 200:1,about 25:1 to about 100:1, about 30:1 to about 60:1, or about 50:1. Thecomposition can include any of these ratios or amounts not modified byabout. These can be weight ratios or ratios of concentration, such asppm. In an embodiment, the compositions do not include a substantialamount of strong acid. In an embodiment, the compositions do not includea substantial amount of mineral acid.

In an embodiment, the present compositions do not include substantialstrong acid. Conventional peroxycarboxylic acid compositions includemineral acid to catalyze the formation of peroxycarboxylic acid fromhydrogen peroxide and carboxylic acid.

Surprisingly, the present inventors have made an effective antimicrobialperoxycarboxylic acid composition without substantial strong acid. Thatis, the present compositions do not include amounts of strong acideffective for catalyzing the reaction of hydrogen peroxide andcarboxylic acid to form peroxycarboxylic acid.

In an embodiment, the present composition is free of strong acid, e.g.,mineral acid. In an embodiment, the present composition is substantiallyfree of strong acid, e.g., mineral acid. In an embodiment, the presentcomposition is free of added strong acid, e.g., mineral acid. In certainembodiments, the present composition includes less than about 5 wt-%strong acid, less than about 4 wt-% strong acid, less than about 3 wt-%strong acid, less than about 2 wt-% strong acid, or less than about 1wt-% strong acid. In an embodiment, the present composition includesless than about 1 wt-% strong acid. The composition can include any ofthese ranges or amounts not modified by about.

In certain embodiments, the present compositions advantageously have loweye corrosivity and/or advantageously masked odor. For example, astorage stable ready to use composition according to the presentinvention can have reduced toxicity compared to conventional concentratecompositions. For example, a storage stable ready to use compositionaccording to the present invention can have its odor masked compared toa conventional concentrate composition that has been diluted with water.

Embodiments of the Present Compositions

Some examples of representative constituent concentrations forembodiments of the present compositions can be found in Tables A-C, inwhich the values are given in wt-% of the ingredients in reference tothe total composition weight. In certain embodiments, the proportionsand amounts in Tables A-C can be modified by “about”.

TABLE A Ingredient wt-% wt-% wt-% wt-% wt-% wt-% peroxy- 0.005-0.2 0.015-0.15  0.03-0.1 0.02-0.12 0.04-0.08 0.06 carboxylic acid shortchain 0.5-4  0.5-3.5 0.5-3  1-3 1.5-2.5 2 carboxylic acid medium chainor 0.01-0.3  0.01-0.25 0.01-0.2 0.04-0.2  0.07-0.15 0.1 aromaticcarboxylic acid oxidizing agent 1-5 2-4 2.5-4  2-4 2.5-3.5 3 optionally,0.01-0.25 0.01-0.2   0.01-0.15 0.01-0.2  0.04-0.08 0.06 corrosioninhibitor

TABLE B Ingredient wt-% wt-% wt-% wt-% wt-% wt-% peroxy-  0.005-0.2 0.015-0.15 0.03-0.1 0.02-0.12 0.04-0.08 0.06 carboxylic acid shortchain  0.5-4   0.5-3.5 0.5-3  1-3 1.5-2.5 2 carboxylic acid medium chainor  0.01-0.3   0.01-0.25 0.01-0.2 0.04-0.2  0.07-0.15 0.1 aromaticcarboxylic acid oxidizing agent   1-5   2-4 2.5-4  2-4 2.5-3.5 3optionally,   0.01-0.25  0.01-0.2  0.01-0.15 0.01-0.2  0.04-0.08 0.06corrosion inhibitor optionally, buffer 0.01-2 0.01-1 0.01-0.8 0.1-0.30.15-0.25 0.2 stabilizing agent 0.01-3 0.01-2 0.01-1  0.04-0.2 0.07-0.15 0.1 hydrotrope 0.01-5 0.01-4 0.01-3  0.04-0.2  0.07-0.15 0.1surfactant 0.01-5 0.01-4 0.01-3  0.1-1  0.3-0.5 0.4

TABLE C Ingredient wt-% wt-% wt-% wt-% wt-% wt-% short chain  0.005-0.20.015-0.15 0.03-0.1  0.02-0.12 0.04-0.08 0.06 peroxy- carboxylic acidmedium chain  0.0001-0.004 0.0001-0.003 0.0001-0.002 0.0001-0.0010.0001-0.0006 0.0001-0.0004 peroxy- carboxylic acid short chain  0.5-4 0.5-3.5 0.5-3   1-3 1.5-2.5 2 carboxylic acid medium chain or  0.01-0.3 0.01-0.25 0.01-0.2 0.04-0.2 0.07-0.15 0.1 aromatic carboxylic acidoxidizing agent   1-5  2-4 2.5-4   2-4 2.5-3.5 3 optionally,   0.01-0.250.01-0.2  0.01-0.15 0.01-0.2 0.04-0.08 0.06 corrosion inhibitoroptionally, buffer 0.01-2 0.01-1  0.01-0.8  0.1-0.3 0.15-0.25 0.2stabilizing agent 0.01-3 0.01-2  0.01-1  0.04-0.2 0.07-0.15 0.1hydrotrope 0.01-5 0.01-4  0.01-3  0.04-0.2 0.07-0.15 0.1 surfactant0.01-5 0.01-4  0.01-3  0.1-1  0.3-0.5 0.4 masking agent 0.01-1 0.01-0.80.01-0.6 0.04-0.2 0.07-0.15 0.1 pH   1-5  1.5-4.5  1.5-3.5  1-4 2.5-3.53The compositions in these Tables can include carrier (e.g., water) tobring the total content up to 100 wt-%.

The compositions in Table C can have one or more advantageous qualitiesincluding: forming a dilute, stable, ready-to-use product; havingenhanced biocidal activity against vegetative bacteria and fungi; havingsignificantly enhanced sporicidal and virucidal activity; providing agood multi-surface detersive cleaner/one-step disinfectant; causing onlylow corrosion against soft metals, plastics and elastomers; being safefor the user (no mineral acid; low dermal, eye & nose irritation);and/or being environmentally friendly.

Unless stated otherwise, the concentrations of ingredients are when thecomposition is at equilibrium. Unless stated otherwise, theconcentrations of ingredients refer to the active component and not toan amount of a commercial product that may include ingredients inaddition to the active ingredient.

In an embodiment, the present antimicrobial composition includes about 2wt-% to about 4 wt-% hydrogen peroxide, about 0.5 wt-% to about 3.5 wt-%acetic acid, about 0.01 wt-% to about 0.25 wt-% octanoic acid, about0.005 wt-% to about 0.15 wt-% of peroxyacetic acid, and about 0.0001wt-% to about 0.002 wt-% peroxyoctanoic acid. In an embodiment, thepresent antimicrobial composition includes about 2.5 wt-% to about 4wt-% hydrogen peroxide, about 0.5 wt-% to about 3 wt-% acetic acid,about 0.01 wt-% to about 0.2 wt-% octanoic acid, about 0.005 wt-% toabout 0.1 wt-% of peroxyacetic acid, and about 0.0001 wt-% to about0.002 wt-% peroxyoctanoic acid.

In an embodiment, the present antimicrobial composition includes about 1wt-% to about 5 wt-% hydrogen peroxide, about 0.5 wt-% to about 4 wt-%acetic acid, about 0.01 wt-% to about 0.3 wt-% octanoic acid, about0.005 wt-% to about 0.2 wt-% peroxyacetic acid, about 0.0001 wt-% toabout 0.004 wt-% peroxyoctanoic acid, about 0.01 wt-% to about 2.5 wt-%sequestering agent, and about 0.01 wt-% to about 1.5 wt-% buffer.

In an embodiment, the present antimicrobial composition includes about 1wt-% to about 5 wt-% hydrogen peroxide, about 0.5 wt-% to about 4 wt-%acetic acid, about 0.01 wt-% to about 0.3 wt-% octanoic acid, about0.005 wt-% to about 0.2 wt-% peroxyacetic acid, about 0.0001 wt-% toabout 0.004 wt-% peroxyoctanoic acid, about 0.01 wt-% to about 2.5 wt-%sequestering agent, about 0.01 wt-% to about 1.5 wt-% buffer, about 0.01wt-% to about 5 wt-% hydrotrope.

In an embodiment, the present antimicrobial composition includes about 1wt-% to about 5 wt-% hydrogen peroxide, about 0.5 wt-% to about 4 wt-%acetic acid, about 0.01 wt-% to about 0.3 wt-% octanoic acid, about0.005 wt-% to about 0.2 wt-% peroxyacetic acid, about 0.0001 wt-% toabout 0.004 wt-% peroxyoctanoic acid, about 0.01 wt-% to about 2.5 wt-%sequestering agent, about 0.01 wt-% to about 1.5 wt-% buffer, about 0.01wt-% to about 5 wt-% hydrotrope and about 0.01 wt-% to about 5 wt-%surfactant.

In an embodiment, the present antimicrobial composition includes about 1wt-% to about 5 wt-% hydrogen peroxide, about 0.5 wt-% to about 4 wt-%acetic acid, about 0.01 wt-% to about 0.3 wt-% octanoic acid, about0.005 wt-% to about 0.2 wt-% peroxyacetic acid, about 0.0001 wt-% toabout 0.004 wt-% peroxyoctanoic acid, about 0.01 wt-% to 2.5 wt-%sequestering agent, about 0.01 wt-% to about 1.5 wt-% buffer, about 0.01wt-% to about 5 wt-% hydrotrope, about 0.01 wt-% to about 5 wt-%surfactant, about 0.01 wt-% to about 0.25 wt-% corrosion inhibitor, andabout 0.01 wt-% to about 1 wt-% masking agent/fragrance.

In an embodiment, the present antimicrobial composition includeshydrogen peroxide, acetic acid, a C₆ to C₁₂ aliphatic carboxylic acidand reaction equilibrium quantities of a peroxyacetic acid and C₆ to C₁₂peroxy carboxylic acid. In an embodiment, the present antimicrobialcomposition includes hydrogen peroxide, peroxyacetic acid, octanoic acidand peroxyoctanoic acid; a ratio of hydrogen peroxide to totalperoxyacid of about 30:1 to about 60:1. In an embodiment, the presentantimicrobial composition includes about 1 wt-% to about 5 wt-% hydrogenperoxide, about 0.5 wt-% to about 4 wt-% acetic acid, about 0.01 wt-% toabout 0.3 wt-% octanoic acid, about 0.005 wt-% to about 0.2 wt-% ofperoxyacetic acid, and about 0.0001 wt-% to about 0.004 wt-%peroxyoctanoic acid.

In an embodiment, the present antimicrobial composition includes a C₆ toC₁₂ aliphatic or an aromatic carboxylic acid and exhibits reducedcorrosion of soft metals at a pH of about 3. Suitable carboxylic acidsinclude hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid,decanoic acid, undecanoic acid, dodecanoic acid, salicylic acid, or amixture thereof. In an embodiment, the present antimicrobial compositionincludes surfactant, which delivers detersive effect upon microbeharboring soils and biofilms preventing such contaminants from shieldingpathogens. In an embodiment, the present antimicrobial compositionincludes a stable odor masking fragrant component uniformly solubilizedby aid of a surfactant. In an embodiment, the present antimicrobialcomposition also includes one or more surfactants, one or moresequestrant stabilizing agents, one or more hydrotropes, one or morefragrances, one or more corrosion inhibiting agents, one or morebuffers, one or more additional adjuvants, water, or a mixture thereof.

The present compositions can be made by combining or mixing at least theingredients required to form peroxycarboxylic acid and letting themreact for a time sufficient to convert carboxylic acid toperoxycarboxylic acid. A sufficient reaction time can be, for example,from a few hours to 21 days.

In an embodiment, the compositions of the present invention include onlyingredients that can be employed in food products or in food wash,handling, or processing, for example, according to government (e.g. FDAor USDA) rules and regulations, 21 CFR §170-178. In an embodiment, thecompositions of the present invention can include only ingredients atthe concentrations approved for incidental food contact by the USEPA, 40CFR §180.940.

The present compositions can take the form of a liquid, gel, paste, unitdose, gel pack, unitized or compartmentalized tear or water solublepacket, or the like. The present compositions can be supplied in any ofa variety of containers or media, such as in a hand held pump/spraycontainer, a 2 compartment dispenser; or as a pre-moistened wipe,towelette, or sponge.

In an embodiment, the concentration of peroxyacetic acid is above 425ppm for the lifetime of a product including an embodiment of acomposition according to the present invention. In an embodiment, theconcentration of octanoic acid is above 900 ppm for a product includingan embodiment of a composition according to the present invention. In anembodiment, the concentration of hydrogen peroxide is above 2.85 wt-%for the lifetime of a product including an embodiment of a compositionaccording to the present invention.

Compositions of Medium Chain Carboxylic Acids and/or PeroxycarboxylicAcids

Peroxycarboxylic (or percarboxylic) acids generally have the formulaR(CO₃H)_(n), where, for example, R is an alkyl, arylalkyl, cycloalkyl,aromatic, or heterocyclic group, and n is one, two, or three, and namedby prefixing the parent acid with peroxy. The R group can be saturatedor unsaturated as well as substituted or unsubstituted. The compositionand methods of the invention can employ medium chain peroxycarboxylicacids containing, for example, 6 to 12 carbon atoms. For example, mediumchain peroxycarboxylic (or percarboxylic) acids can have the formulaR(CO₃H)_(n), where R is a C₅-C₁₁ alkyl group, a C₅-C₁₁ cycloalkyl, aC₅-C₁₁ arylalkyl group, C₅-C₁₁ (e.g., C₆) aryl group, or a C₅-C₁₁heterocyclic group; and n is one, two, or three.

Peroxycarboxylic acids can be made by the direct action of an oxidizingagent on a carboxylic acid, by autoxidation of aldehydes, or from acidchlorides, and hydrides, or carboxylic anhydrides with hydrogen orsodium peroxide. In an embodiment, the medium chain percarboxylic acidscan be made by the direct, acid catalyzed equilibrium action of hydrogenperoxide on the medium chain carboxylic acid. Scheme 1 illustrates anequilibrium between carboxylic acid and oxidizing agent (Ox) on one sideand peroxycarboxylic acid and reduced oxidizing agent (Oxred) on theother:

RCOOH+Ox

RCOOOH+Ox_(red)  (1)

Scheme 2 illustrates an embodiment of the equilibrium of scheme 1 inwhich the oxidizing agent is hydrogen peroxide on one side andperoxycarboxylic acid and water on the other:

RCOOH+H₂O₂

RCOOOH+H₂O  (2)

In conventional mixed peroxycarboxylic acid compositions it is believedthat the equilibrium ratio for the reaction illustrated in scheme 2 isabout 2.5, which may reflect the equilibrium for acetic acid.

Peroxycarboxylic acids useful in the compositions and methods of thepresent invention include peroxypentanoic, peroxyhexanoic,peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic,peroxyundecanoic, peroxydodecanoic, peroxysalicylic acid, peroxybenzoicacid, mixtures thereof, or the like. The alkyl backbones of the mediumchain peroxycarboxylic acid can be straight chain, branched, or amixture thereof. Peroxy forms of carboxylic acids with more than onecarboxylate moiety can have one or more (e.g., at least one) of thecarboxyl moieties present as peroxycarboxyl moieties.

Peroxyoctanoic (or peroctanoic) acid is a peroxycarboxylic acid havingthe formula, for example, of n-peroxyoctanoic acid: CH₃(CH₂)₆COOOH.Peroxyoctanoic acid can be an acid with a straight chain alkyl moiety,an acid with a branched alkyl moiety, or a mixture thereof.Peroxyoctanoic acid is surface active and can assist in wettinghydrophobic surfaces, such as those of microbes.

The composition of the present invention can include a carboxylic acid.Generally, carboxylic acids have the formula R—COOH wherein the R canrepresent any number of different groups including aliphatic groups,alicyclic groups, aromatic groups, heterocyclic groups, all of which canbe saturated or unsaturated as well as substituted or unsubstituted.Carboxylic acids can have one, two, three, or more carboxyl groups. Thecomposition and methods of the invention typically employ medium chaincarboxylic acids containing, for example, 6 to 12 carbon atoms. Forexample, medium chain carboxylic acids can have the formula R—COOH inwhich R can be a C₅-C₁₁ alkyl group, a C₅-C₁₁ cycloalkyl group, a C₅-C₁₁arylalkyl group, C₅-C₁₁ (e.g., C₆) aryl group, or a C₅-C₁₁ heterocyclicgroup.

Suitable medium chain carboxylic acids include pentanoic acid, hexanoicacid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid,undecanoic acid, dodecanoic acid, salicylic acid, benzoic acid, mixturesthereof, or the like. The alkyl backbones of the medium chain carboxylicacids can be straight chain, branched, or a mixture thereof. Carboxylicacids which are generally useful are those having one or two carboxylgroups where the R group is a primary alkyl chain having a length of C₄to C₁₁. The primary alkyl chain is that carbon chain of the moleculehaving the greatest length of carbon atoms and directly appendingcarboxyl functional groups. Carboxylic acids which are generally usefulare those having one carboxyl group as a substituent on a phenyl ring,such as salicylic acid or benzoic acid.

The present compositions and methods can include a medium chainperoxycarboxylic acid. The medium chain peroxycarboxylic acid caninclude or be a C6 to C12 peroxycarboxylic acid. The C6 to C12peroxycarboxylic acid can include or be peroxyhexanoic acid,peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid,peroxydecanoic acid, peroxyundecanoic acid, peroxydodecanoic acid, ormixture thereof. The medium chain peroxycarboxylic acid can include orbe a C7 to C12 peroxycarboxylic acid. The C7 to C12 peroxycarboxylicacid can include or be peroxyheptanoic acid, peroxyoctanoic acid,peroxynonanoic acid, peroxydecanoic acid, peroxyundecanoic acid,peroxydodecanoic acid, or mixture thereof. The medium chainperoxycarboxylic acid can include or be a C6 to C10 peroxycarboxylicacid. The C6 to C10 peroxycarboxylic acid can include or beperoxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid,peroxynonanoic acid, peroxydecanoic acid, or mixture thereof. The mediumchain peroxycarboxylic acid can include or be a C8 to C10peroxycarboxylic acid. The C8 to C10 peroxycarboxylic acid can includeor be peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, ormixture thereof. In certain embodiments, the medium chain peroxyoctanoicacid includes or is peroxyoctanoic acid, peroxydecanoic acid, or mixturethereof. In an embodiment, the medium chain peroxycarboxylic acidincludes or is peroxyoctanoic acid.

In certain embodiments, a composition of the invention can includes oneor more peroxycarboxylic acids such as peroxyacetic acid, peroxyhexanoicacid, peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid,peroxydecanoic acid, peroxyundecanoic acid, peroxydodecanoic acid,peroxysalicylic acid and peroxybenzoic acid. Such a peroxycarboxylicacid can be at a concentration of 0.001 to about 0.2 wt-%, about 0.005wt-% to about 0.2 wt-%, about 0.005 wt-% to about 0.15 wt-%, or about0.005 wt-% to about 0.1 wt-%. In an embodiment, the composition of theinvention includes hydrogen peroxide and peroxycarboxylic acid at aratio of hydrogen peroxide to total peroxycarboxylic acid about 10:1 toabout 200:1, about 25:1 to about 100:1, about 30:1 to about 60:1, orabout 50:1. This ratio can be based on weight percent or parts permillion of total peroxycarboxylic acids present. The composition caninclude any of these ranges or amounts not modified by about. In anembodiment, the composition of the invention includes peroxyacetic acidand peroxyoctanoic acid.

In an embodiment, the present compositions and methods include a mediumchain carboxylic acid. The medium chain carboxylic acid can include orbe a C6 to C12 carboxylic acid. The C6 to C12 carboxylic acid caninclude or be hexanoic acid, heptanoic acid, octanoic acid, nonanoicacid, decanoic acid, undecanoic acid, dodecanoic acid, or mixturethereof. The medium chain carboxylic acid can include or be a C7 to C12carboxylic acid. The C7 to C12 carboxylic acid can include or beheptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoicacid, dodecanoic acid, or mixture thereof. The medium chain carboxylicacid can include or be a C6 to C10 carboxylic acid. The C6 to C10carboxylic acid can include or be hexanoic acid, heptanoic acid,octanoic acid, nonanoic acid, decanoic acid, or mixture thereof. Themedium chain carboxylic acid can include or be a C8 to C10 carboxylicacid. The C8 to C10 carboxylic acid can include or be octanoic acid,nonanoic acid, decanoic acid, or mixture thereof. In certainembodiments, the medium chain carboxylic acid includes or is octanoicacid, decanoic acid, or mixture thereof. In an embodiment, the mediumchain carboxylic acid includes or is octanoic acid. In an embodiment,the medium chain carboxylic acid includes or is salicylic acid.

The compositions can include an aliphatic medium chain mono carboxylicacid such as hexanoic acid, heptanoic acid, octanoic acid, or nonanoicacid; or a benzoic acid derivative. As used herein, the phrase “benzoicacid derivative” refers to benzoic acid and ring substituted benzoicacids (e.g., salicylic acid). These carboxylic acids effectively augmentthe reduction in corrosion in the presence of a corrosion inhibitor atacid pH, e.g., pH of about 1 to about 5, about 1 to about 4.5, or about1 to about 4. The composition can include such a carboxylic acid and acorrosion inhibitor, such as a triazole corrosion inhibitor. Thecomposition can include such a carboxylic acid at a concentration ofabout 0.01 to about 0.2 wt-%, about 0.01 to about 5 wt-%, about 0.5 wt-%to about 4 wt-%, about 0.5 wt-% to about 3 wt-%. The composition caninclude any of these ranges or amounts not modified by about.

In an embodiment, the compositions and methods include a medium chainperoxycarboxylic acid and the corresponding medium chain carboxylicacid.

In an embodiment, the present composition includes an amount of mediumchain carboxylic acid effective for killing one or more (e.g., at leastone) of the food-borne pathogenic bacteria associated with a foodproduct, such as Salmonella typhimurium, Salmonella javiana,Campylobacter jejuni, Listeria monocytogenes, and Escherichia coliO157:H7, yeast, mold, and the like. In an embodiment, the presentcomposition includes an amount of medium chain carboxylic acid effectivefor killing one or more (e.g., at least one) of the pathogenic bacteriaassociated with a health care surfaces and environments, such asSalmonella typhimurium, Staphylococcus aureus, Salmonella choleraesurus,Pseudomonas aeruginosa, Escherichia coli, mycobacteria, yeast, mold,antibiotic resistant Staphylococcus (MRSA, VISA), community acquiredantibiotic resistant Staphylococcus species, and the like. Thecompositions and methods of the present invention have activity againsta wide variety of microorganisms such as Gram positive (for example,Listeria monocytogenes or Staphylococcus aureus) and Gram negative (forexample, Escherichia coli or Pseudomonas aeruginosa) bacteria, yeast,molds, bacterial spores, viruses, etc. The compositions and methods ofthe present invention, as described above, have activity against a widevariety of human pathogens. The present compositions and methods cankill a wide variety of microorganisms on a food processing surface, onthe surface of a food product, in water used for washing or processingof food product, on a health care surface, or in a health careenvironment.

Compositions of Short Chain Carboxylic Acids and/or PeroxycarboxylicAcids

The composition and methods of the invention can employ short chainperoxycarboxylic acids containing, for example, 1 to 4 carbon atoms. Forexample, short chain peroxycarboxylic (or percarboxylic) acids can havethe formula R(CO₃H)_(n), where R is H or a C₁-C₃ alkyl group and n isone, two, or three. In an embodiment, the short chain percarboxylicacids can be made by the direct, acid catalyzed equilibrium action ofhydrogen peroxide on the short chain carboxylic acid. In conventionalmixed peroxycarboxylic acid compositions it is believed that theequilibrium constant for the reaction illustrated in scheme 2 is about2.5, which may reflect the equilibrium for acetic acid.

Peroxycarboxylic acids useful in the compositions and methods of thepresent invention include peroxyformic acid, peroxyacetic acid,peroxypropionic acid, and peroxybutyric acid, mixtures thereof, or thelike. The alkyl backbones of certain of the propionic and butyricperoxycarboxylic acids can be straight chain, branched, or a mixturethereof. Peroxy forms of carboxylic acids with more than one carboxylatemoiety can have one or more (e.g., at least one) of the carboxylmoieties present as peroxycarboxyl moieties. Peroxyacetic (or peracetic)acid is a peroxycarboxylic acid having the formula: CH₃COOOH. In anembodiment, the short chain peroxycarboxylic acid includes or isperoxyacetic acid.

The composition of the present invention can include a short chaincarboxylic acid. The composition and methods of the invention typicallyemploy short chain carboxylic acids containing, for example, 2 to 4carbon atoms. For example, short chain carboxylic acids can have theformula R—COOH in which R can be a H or a C₁-C₃ alkyl group. Suitableshort chain carboxylic acids include formic acid, acetic acid, propionicacid, and butyric acid, mixtures thereof, or the like. The alkylbackbones propionic acid and butyric acid can be straight chain,branched, or a mixture thereof. In an embodiment, the short chaincarboxylic acid is a hydroxycarboxylic acid (e.g., anα-hydroxycarboxylic acid), such as hydroxyacetic acid orhydroxypropionic acid. In an embodiment, the short chain carboxylic acidincludes or is acetic acid. In an embodiment, the compositions andmethods include a short chain peroxycarboxylic acid and thecorresponding short chain carboxylic acid.

In an embodiment, the present composition includes an amount of shortchain peroxycarboxylic acid effective for killing one or more (e.g., atleast one) of the food-borne pathogenic bacteria associated with a foodproduct, such as Salmonella typhimurium, Salmonella javiana,Campylobacter jejuni, Listeria monocytogenes, and Escherichia coliO157:H7, yeast, mold, and the like. In an embodiment, the presentcomposition includes an amount of short chain peroxycarboxylic acideffective for killing one or more (e.g., at least one) of the pathogenicbacteria associated with a health care surfaces and environments, suchas Salmonella typhimurium, Staphylococcus aureus, Salmonellacholeraesurus, Pseudomonas aeruginosa, Escherichia coli, mycobacteria,yeast, mold, antibiotic resistant Staphylococcus (MRSA, VISA), communityacquired antibiotic resistant Staphylococcus species, and the like. Thecompositions and methods of the present invention have activity againsta wide variety of microorganisms such as Gram positive (for example,Listeria monocytogenes or Staphylococcus aureus) and Gram negative (forexample, Escherichia coli or Pseudomonas aeruginosa) bacteria, yeast,molds, bacterial spores, viruses, etc. The compositions and methods ofthe present invention, as described above, have activity against a widevariety of human pathogens. The present compositions and methods cankill a wide variety of microorganisms on a food processing surface, onthe surface of a food product, in water used for washing or processingof food product, on a health care surface, or in a health careenvironment.

Oxidizing Agent

The present compositions and methods can include any of a variety ofoxidizing agents. The oxidizing agent can be used for maintaining orgenerating peroxycarboxylic acids. Hydrogen peroxide presents onesuitable example of an inorganic oxidizing agent. Hydrogen peroxide canbe provided as a mixture of hydrogen peroxide and water, e.g., as liquidhydrogen peroxide in an aqueous solution. Hydrogen peroxide iscommercially available at concentrations of 35%, 70%, and 90% in water.For safety, the 35% is commonly used. The present compositions caninclude, for example, about 2 to about 30 wt-% or about 5 to about 20wt-% hydrogen peroxide.

In an embodiment, the present compositions and methods can includehydrogen peroxide, urea peroxide, or cumene hydroperoxide as oxidizingagent. Hydrogen peroxide in combination with the percarboxylic acid canprovide certain antimicrobial action against microorganisms.Additionally, hydrogen peroxide can provide an effervescent action whichcan irrigate any surface to which it is applied. Hydrogen peroxide canwork with a mechanical flushing action once applied which further cleansthe surface of an object. An additional advantage of hydrogen peroxideis the food compatibility of this composition upon use anddecomposition. An oxidizing agent different from hydrogen peroxide canbe employed at a concentration that provides equivalent oxidation oroxygen concentrations.

In certain embodiments, the composition of the present inventionincludes hydrogen peroxide (or another oxidizing agent) at about 0.3 toabout 5% wt-%, about 1 wt-% to about 5 wt-%, about 2 wt-% to about 4wt-%, or about 2.5 wt-% to about 4 wt-%. The composition can include anyof these ranges or amounts not modified by about.

Carrier

The composition of the invention can also include a carrier. The carrierprovides a medium which dissolves, suspends, or carries the othercomponents of the composition. For example, the carrier can provide amedium for solubilization, suspension, or production of peroxycarboxylicacid and for forming an equilibrium mixture. The carrier can alsofunction to deliver and wet the antimicrobial composition of theinvention on an object. To this end, the carrier can contain anycomponent or components that can facilitate these functions.

In certain embodiments, the carrier includes primarily water which canpromote solubility and work as a medium for reaction and equilibrium.The carrier can include or be primarily an organic solvent. Polyols canbe useful carriers, including glycerol, sorbitol, and the like.

Suitable carriers include glycol ethers. Glycol ethers includediethylene glycol n-butyl ether, diethylene glycol n-propyl ether,diethylene glycol ethyl ether, diethylene glycol methyl ether,diethylene glycol t-butyl ether, dipropylene glycol n-butyl ether,dipropylene glycol methyl ether, dipropylene glycol ethyl ether,dipropylene glycol propyl ether, dipropylene glycol tert-butyl ether,ethylene glycol butyl ether, ethylene glycol propyl ether, ethyleneglycol ethyl ether, ethylene glycol methyl ether, ethylene glycol methylether acetate, propylene glycol n-butyl ether, propylene glycol ethylether, propylene glycol methyl ether, propylene glycol n-propyl ether,tripropylene glycol methyl ether and tripropylene glycol n-butyl ether,ethylene glycol phenyl ether (commercially available as DOWANOL EPH™from Dow Chemical Co.), propylene glycol phenyl ether (commerciallyavailable as DOWANOL PPH™ from Dow Chemical Co.), and the like, ormixtures thereof. Additional suitable commercially available glycolethers (all of which are available from Union Carbide Corp.) includeButoxyethyl PROPASOL™, Butyl CARBITOL™ acetate, Butyl CARBITOL™, ButylCELLOSOLVE™ acetate, Butyl CELLOSOLVE™, Butyl DIPROPASOL™, ButylPROPASOL™, CARBITOL™ PM-600, CARBITOL™ Low Gravity, CELLOSOLVE™ acetate,CELLOSOLVE™, Ester EEP™ FILMER IBT™, Hexyl CARBITOL™, Hexyl CELLOSOLVE™,Methyl CARBITOL™, Methyl CELLOSOLVE™ acetate, Methyl CELLOSOLVE™, MethylDIPROPASOL™ Methyl PROPASOL™ acetate, Methyl PROPASOL™, PropylCARBITOL™, Propyl CELLOSOLVE™, Propyl DIPROPASOL™ and Propyl PROPASOL™.

In certain embodiments, the carrier makes up a large portion of thecomposition of the invention and may be the balance of the compositionapart from the active antimicrobial components, solubilizer, oxidizingagent, adjuvants, and the like. Here again, the carrier concentrationand type will depend upon the nature of the composition as a whole, theenvironmental storage, and method of application including concentrationof the peroxycarboxylic acid, among other factors. Notably the carriershould be chosen and used at a concentration which does not inhibit theantimicrobial efficacy of the peroxycarboxylic acid in the compositionof the invention.

In certain embodiments, the present composition includes about 60 toabout 99 wt-% carrier (e.g., water), about 70 to about 99 wt-% carrier(e.g., water), about 80 to about 97 wt-% carrier (e.g., water), about 85to about 95 wt-% carrier (e.g., water), or about 90 to about 95 wt-%carrier (e.g., water). For example, in certain embodiments, the presentcomposition can include about 70 wt-% carrier (e.g., water), about 75wt-% carrier (e.g., water), about 80 wt-% carrier (e.g., water), about85 wt-% carrier (e.g., water), about 90 wt-% carrier (e.g., water), orabout 95 wt-% carrier (e.g., water).

Buffer

The present composition can include a buffer, such as a buffer effectiveto maintain the pH of the composition at an acid pH, e.g., about 1 toabout 5, about 1 to about 4.5, or about 1 to about 4. Buffers suitablefor such acid pHs are or include 3-(N-morpholino)propanesulfonic acid(MOPS), piperazine-N,N′-bis(2-ethanesulfonic acid) (PIPES),2-(N-morpholino)ethanesulfonic acid (MES), N-(2-Acetamido)iminodiaceticAcid (ADA), sodium phosphate, sodium citrate, sodium formate, sodiummalate, sodium acetate, or sodium diacetate. Suitable buffers are orinclude phosphate salt, citrate salt, formate salt, malate salt, oracetate salt. Suitable buffers are or include sodium phosphate, sodiumcitrate, sodium formate, sodium malate, or sodium acetate. A suitablebuffer is or includes acetic acid and acetate (e.g., sodium acetate).

The present compositions can include the salt component of the bufferat, for example, about 0.01 to about 1.5 wt-%, about 0.05 to about 1wt-%, or about 0.05 wt-% to about 0.8 (e.g., 0.75) wt-%. In certainembodiments, the present composition includes sodium acetate at about0.01 to about 1.5 wt-%, about 0.05 to about 1 wt-%, or about 0.05 wt-%to about 0.8 (e.g., 0.75) wt-%.

Corrosion Inhibitor

The composition of the present invention can include a corrosioninhibitor. Suitable corrosion inhibitors include triazoles, such asbenzotriazole (CAS no. 95-14-7) or tolytriazole (CAS no. 64665-57-2). Atriazole corrosion inhibitor, such as benzotriazole, can be included ata concentration of about 0.01 to about 0.25 wt-%, about 0.01 to about0.2 wt-%, or about 0.01 wt-% to about 0.15 wt-%.

Adjuvants

The antimicrobial composition of the invention can also include anynumber of adjuvants. Specifically, the composition of the invention caninclude stabilizing agent, antimicrobial agent, wetting agent, defoamingagent, thickener, a surfactant, foaming agent, a hydrotrope or couplingagent, a surfactant, aesthetic enhancing agent (i.e., colorant (e.g.,pigment), odorant, perfume, fragrance, or masking agent), among anynumber of constituents which can be added to the composition. Suchadjuvants can be preformulated with the antimicrobial composition of theinvention or added to the system simultaneously, or even after, theaddition of the antimicrobial composition. Additional suitable adjuvantsinclude potentiators (also referred to as synergists to the activeingredients) rheology modifiers, manufacturing processing aids,preserving agents, or tracers. The composition of the invention can alsocontain any number of other constituents as necessitated by theapplication, which are known and which can facilitate the activity ofthe present invention.

An adjuvant can be selected to be compatible with the other componentsin the composition in the long term, for at least 6 months andpreferably at least 12 months or longer at ambient room temperatures.

Stabilizing Agent

One or more stabilizing agents can be added to the composition of theinvention, for example, to stabilize the peracid and hydrogen peroxideand prevent the premature degradation of this constituent within thecomposition of the invention.

Suitable stabilizing agents include chelating agents or sequestrants.Suitable sequestrants include organic chelating compounds that sequestermetal ions in solution, particularly transition metal ions. Suchsequestrants include organic amino- or hydroxy-polyphosphonic acidcomplexing agents (either in acid or soluble salt forms), carboxylicacids (e.g., polymeric polycarboxylate), hydroxycarboxylic acids, oraminocarboxylic acids.

The sequestrant can be or include phosphonic acid or phosphonate salt.Suitable phosphonic acids and phosphonate salts include 1-hydroxyethylidene-1,1-diphosphonic acid (CH₃C(PO₃H₂)₂OH) (HEDP);ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; or mixtures thereof.

Suitable organic phosphonates include HEDP

Commercially available food additive chelating agents includephosphonates sold under the trade name DEQUEST® including, for example,1-hydroxyethylidene-1,1-diphosphonic acid, available from MonsantoIndustrial Chemicals Co., St. Louis, Mo., as DEQUEST® 2010;amino(tri(methylenephosphonic acid)), (N[CH₂PO₃H₂]₃), available fromMonsanto as DEQUEST® 2000; ethylenediamine[tetra(methylenephosphonicacid)] available from Monsanto as DEQUEST® 2041; and2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay ChemicalCorporation, Inorganic Chemicals Division, Pittsburgh, Pa., as BayhibitAM.

In certain embodiments, the present composition includes stabilizingagent at about 0.01 to about 3 (e.g., 2.5) wt-%, about 0.01 to about 2(e.g., 2.5) wt-%, or about 0.01 to about 1.5 wt-%. The composition caninclude any of these ranges or amounts not modified by about.

Additional Antimicrobial Agent

The antimicrobial compositions of the invention can contain anadditional antimicrobial agent. Additional antimicrobial agent can beadded to use compositions before use. Suitable antimicrobial agentsinclude sulfonic acids (e.g., dodecylbenzene sulfonic acid), phenolicderivatives (e.g., o-phenyl phenol, o-benzyl-p-chlorophenol, tert-amylphenol and C₁-C₆ alkyl hydroxy benzoates), quaternary ammonium compounds(e.g., alkyldimethylbenzyl ammonium chloride, dialkyldimethyl ammoniumchloride, N-dialkylethylbenzyl ammonium chloride, or mixtures thereof),and mixtures of such antimicrobial agents, in an amount sufficient toprovide the desired degree of microbial protection.

The present composition can include an effective amount of antimicrobialagent, such as about 0.001 wt-% to about 10 wt-% antimicrobial agent,about 0.003 wt-% to about 5 wt-% antimicrobial agent, or about 0.01 wt-%to about 2.5 wt-% antimicrobial agent.

Wetting or Defoaming Agents

Also useful in the composition of the invention are wetting anddefoaming agents. Wetting agents function to increase the surfacecontact or penetration activity of the antimicrobial composition of theinvention. Wetting agents which can be used in the composition of theinvention include any of those constituents known within the art toraise the surface activity of the composition of the invention.

Suitable defoamers which can be used in accordance with the inventioninclude aliphatic acids or esters; alcohols; sulfates or sulfonates;amines or amides; vegetable oils, waxes, mineral oils as well as theirsulfated derivatives; fatty acid soaps such as alkali, alkaline earthmetal soaps; and mixtures thereof.

In an embodiment, the present compositions can include antifoamingagents or defoamers which are of food grade quality given theapplication of the method of the invention. To this end, one of the moreeffective antifoaming agents includes silicones. Silicones such asdimethyl silicone, glycol polysiloxane, methylphenol polysiloxane,trialkyl or tetralkyl silanes, hydrophobic silica defoamers and mixturesthereof can all be used in defoaming applications. Commercial defoamerscommonly available include silicones such as Ardefoam® from ArmourIndustrial Chemical Company which is a silicone bound in an organicemulsion; Foam Kill® or Kresseo® available from Krusable ChemicalCompany which are silicone and non-silicone type defoamers as well assilicone esters; and Anti-Foam A® and DC-200 from Dow CorningCorporation which are both food grade type silicones among others. Thesedefoamers can be present at a concentration range of about 0.01 wt-% to5 wt-%, about 0.01 wt-% to 2 wt-%, or about 0.01 wt-% to about 1 wt-%.

Thickening or Gelling Agents

The present compositions can include any of a variety of knownthickeners. Suitable thickeners include inorganic thickeners, organicthickeners, oligomeric thickeners, and associative thickeners. These mayinclude natural gums such as xanthan gum, guar gum, or other gums fromplant mucilage; modified cellulose derivatives; oligomeric organicthickeners; and hydrocolloid thickeners, such as pectin and inorganicsilicates and clays. In an embodiment, the thickener does not leavecontaminating residue on the surface of an object. For example, thethickeners or gelling agents can be compatible with food or othersensitive products in contact areas. Generally, the concentration ofthickener employed in the present compositions or methods will bedictated by the desired viscosity of the final composition. However, asa general guideline, the quantity of thickener suitable for use in thepresent composition ranges about 0.1 wt-% to about 1.5 wt-%, about 0.1wt-% to about 1 wt-%, or about 0.1 wt-% to about 0.5 wt-%.

Hydrotrope or Coupling Agent

A composition of the invention can also include a hydrotrope, alsoreferred to as a coupling agent. A hydrotrope can increase themiscibility, solubility or phase stability of organic and inorganicmaterials in aqueous solution. A hydrotrope can also facilitate longterm physical stability and/or homogenicity of a composition of theinvention. A hydrotrope can be useful in a composition containing acarboxylic acid or peroxycarboxylic acid.

Suitable hydrotropes include nonaqueous liquid carriers or solvents.Suitable solvents include propylene oxide glycol ether (for example, aDowanol® P Series (Dow Chemical, Midland, Mich.)) or an ethylene oxidebased glycol ether. Suitable propylene oxide glycols include adipropylene glycol n-propyl ether sold under the tradename Dowanol DPnBby Dow Chemical.

A stabilizing hydrotrope or coupling agent can be present in thecomposition at, for example, about 0.01 to about 5 wt-%, about 0.05 toabout 4 wt-%, or about 0.05 to about 3 wt-%.

Surfactant

A composition of the invention may include a surfactant. Suitablesurfactants include water-soluble or water dispersible nonionic,cationic, amphoteric, semipolar nonionic (e.g., zwitterionic) surfaceactive agents.

The surfactant can be a nonionic surfactant. Suitable nonionicsurfactant include a surfactant with ethylene oxide moieties, propyleneoxide moieties or mixtures thereof, and surfactants with ethyleneoxide-propylene oxide moieties in heretic, block or random heretic-blockformation. Suitable nonionic surfactants include alkyl ethylene oxidesurfactants, alkyl propylene oxide surfactants, alkyl ethyleneoxide-propylene oxide surfactants, and alkyl ethylene oxide-propyleneoxide surfactants in which the ethylene oxide-propylene oxide moiety iseither in heretic, block or random heretic-block formation.

The nonionic surfactants can be a nonionic surfactant having any mixtureor combination of ethylene oxide-propylene oxide moieties linked to analkyl chain where the ethylene oxide and propylene oxide moieties may bein any randomized or ordered pattern and of any specific length.Nonionic moieties may be capped/terminated with a benzyl, alkoxy orshort chain alkyl grouping.

The nonionic surfactants can be a condensation product of a saturated orunsaturated, straight or branched chain alcohol having from about 6 to24 carbon atoms with about 3 to about 50 moles of ethylene oxide. Thealcohol moiety can consist of mixtures of alcohols in the abovedelineated carbon range or it can consist of an alcohol having aspecific number of carbon atoms within this range. Examples ofcommercial surfactants of this chemistry are available under the tradename of Surfonic® manufactured by Huntsman Corp., Austin, Tex. andNeodol® manufactured by Shell Chemical Co., Houston, Tex.

A surfactant or surfactant system employed in the composition of thepresent invention can be present at about 0.01 to about 5 wt-%, about0.01 to about 4 wt-%, or about 0.01 to about 3 wt-%.

Fragrance or Masking Agent

In an embodiment, the present composition includes a fragrance ormasking agent. The fragrance can be selected to avoid undesirableeffects on the stability or efficacy of the composition. A masking agentis one or more fragrant ingredients that mask or conceal an irritatingodor, such as that of acetic acid or peroxyacetic acid. In anembodiment, the masking agent is chemically stable in highly oxidativeacidic systems for at least about 6 months at typical room temperatures(20-25° C.), or even at least about 12 months, 24 months, or longer.Suitable masking agents include Fragrance WS 22201 Clean Herbal Mod II®,manufactured by Wessels Fragrance, Englewood Cliffs, N.J.; Snappy AppleUP183078® and, Wintermint UP183077® manufactured by Givaudan Fragrance,Teaneck, N.J. The masking agent can be included at a concentration ofabout 0.01 to about 1 wt-%, about 0.01 to about 0.8 wt-%, or about 0.01wt-% to about 0.5 wt-%.

Use Compositions

The present compositions include concentrate compositions and usecompositions. For example, a concentrate composition can be diluted, forexample with water, to form a use composition. In an embodiment, aconcentrate composition can be diluted to a use solution before toapplication to an object. For reasons of economics, the concentrate canbe marketed and an end user can dilute the concentrate with water or anaqueous diluent to a use solution.

The level of active components in the concentrate composition isdependent on the intended dilution factor and the desired activity ofthe peroxycarboxylic acid compound. Generally, a dilution of about 1fluid ounce to about 20 gallons of water to about 5 fluid ounces toabout 1 gallon of water is used for aqueous antimicrobial compositions.Higher use dilutions can be employed if elevated use temperature(greater than 25° C.) or extended exposure time (greater than 30seconds) can be employed. In the typical use locus, the concentrate isdiluted with a major proportion of water using commonly available tap orservice water mixing the materials at a dilution ratio of about 3 toabout 20 ounces of concentrate per 100 gallons of water.

For example, a use composition can include about 0.01 to about 4 wt-% ofa concentrate composition and about 96 to about 99.99 wt-% diluent;about 0.5 to about 4 wt-% of a concentrate composition and about 96 toabout 99.5 wt-% diluent; about 0.5, about 1, about 1.5, about 2, about2.5, about 3, about 3.5, or about 4 wt-% of a concentrate composition;about 0.01 to about 0.1 wt-% of a concentrate composition; or about0.01, about 0.02, about 0.03, about 0.04, about 0.05, about 0.06, about0.07, about 0.08, about 0.09, or about 0.1 wt-% of a concentratecomposition. Amounts of an ingredient in a use composition can becalculated from the amounts listed above for concentrate compositionsand these dilution factors.

Methods Employing the Present Peroxycarboxylic Acid Compositions

The present invention includes methods employing the peroxycarboxylicacid compositions. Typically, these methods employ the antimicrobial orbleaching activity of the peroxycarboxylic acid. For example, theinvention includes a method for reducing a microbial population, amethod for reducing the population of a microorganism on skin, a methodfor treating a disease of skin, a method for reducing an odor, or amethod for bleaching. These methods can operate on an object, surface,in a body or stream of water or a gas, or the like, by contacting theobject, surface, body, or stream with a stabilized esterperoxycarboxylic acid composition of the invention. Contacting caninclude any of numerous methods for applying a composition, such asspraying the composition, immersing the object in the composition, foamor gel treating the object with the composition, or a combinationthereof.

The compositions of the invention can be used for a variety of domesticor industrial applications, e.g., to reduce microbial or viralpopulations on a surface or object or in a body or stream of water. Thecompositions can be applied in a variety of areas including kitchens,bathrooms, factories, hospitals, dental offices and food plants, and canbe applied to a variety of hard or soft surfaces having smooth,irregular or porous topography. Suitable hard surfaces include, forexample, architectural surfaces (e.g., floors, walls, windows, sinks,tables, counters and signs); eating utensils; hard-surface medical orsurgical instruments and devices; and hard-surface packaging. Such hardsurfaces can be made from a variety of materials including, for example,ceramic, metal, glass, wood or hard plastic. Suitable soft surfacesinclude, for example paper; filter media, hospital and surgical linensand garments; soft-surface medical or surgical instruments and devices;and soft-surface packaging. Such soft surfaces can be made from avariety of materials including, for example, paper, fiber, woven ornonwoven fabric, soft plastics and elastomers. The compositions of theinvention can also be applied to soft surfaces such as food and skin(e.g., a hand). The present compositions can be employed as a foaming ornonfoaming environmental sanitizer or disinfectant.

The antimicrobial compositions of the invention can be included inproducts such as sterilants, sanitizers, disinfectants, preservatives,deodorizers, antiseptics, fungicides, germicides, sporicides, virucides,detergents, bleaches, and hard surface cleaners.

The antimicrobial compositions can also be used in veterinary productssuch as mammalian skin treatments or in products for sanitizing ordisinfecting animal enclosures, pens, watering stations, and veterinarytreatment areas such as inspection tables and operation rooms. Thepresent compositions can be employed in an antimicrobial foot bath forlivestock or as a boot or shoe sole dip for people.

The present compositions can be employed for reducing the population ofpathogenic microorganisms, such as pathogens of humans, animals, and thelike. The compositions can exhibit activity against pathogens includingfungi, molds, bacteria, spores, and viruses, for example, Trycophytonsp., Aspergillus sp., Staphylococcus sp., antibiotic resistantStaphylococcus sp., E. coli, Streptococcus sp., Enterococcus sp.,Legionella sp., Pseudomonas sp., Mycobacterium sp., Clostridium sp.,influenza and hepatitis viruses, phages, and the like. Such pathogenscan cause a variety of diseases and disorders, including tuberculosis,lung and tissue infections, septicemic infections, hemolyticgastroenteritis, influenza, hepatitis, and the like. The compositions ofthe present invention can reduce the population of microorganisms onskin or other external or mucosal surfaces of an animal. In addition,the present compositions can kill pathogenic microorganisms that spreadthrough transfer by water, air, or a surface substrate. The compositionneed only be applied to the skin, other external or mucosal surfaces ofan animal water, air, or surface.

The antimicrobial compositions can also be used on foods and plantspecies to reduce surface microbial populations; used at manufacturingor processing sites handling such foods and plant species; or used totreat process waters around such sites. For example, the compositionscan be used on food transport lines (e.g., as belt sprays); boot andhand-wash dip-pans; food storage facilities; anti-spoilage aircirculation systems; refrigeration and cooler equipment; beveragechillers and warmers, blanchers, cutting boards, third sink areas, andmeat chillers or scalding devices. The compositions of the invention canbe used to treat produce transport waters such as those found in flumes,pipe transports, cutters, slicers, blanchers, retort systems, washers,and the like. Particular foodstuffs that can be treated withcompositions of the invention include eggs, meats, seeds, leaves, fruitsand vegetables. Particular plant surfaces include both harvested andgrowing leaves, roots, seeds, skins or shells, stems, stalks, tubers,corms, fruit, and the like. The compositions may also be used to treatanimal carcasses to reduce both pathogenic and non-pathogenic microbiallevels.

The present composition is useful in the cleaning or sanitizing ofcontainers, processing facilities, or equipment in the food service orfood processing industries. The antimicrobial compositions can be usedon food packaging materials and equipment, and especially for cold orhot aseptic packaging. Examples of process facilities in which thecomposition of the invention can be employed include a milk line dairy,a continuous brewing system, food processing lines such as pumpable foodsystems and beverage lines, etc. Food service wares can be disinfectedwith the composition of the invention. For example, the compositions canalso be used on or in ware wash machines, dishware, bottle washers,bottle chillers, warmers, third sink washers, cutting areas (e.g., waterknives, slicers, cutters and saws) and egg washers. Particular treatablesurfaces include packaging such as cartons, bottles, films and resins;dish ware such as glasses, plates, utensils, pots and pans; ware washmachines; exposed food preparation area surfaces such as sinks,counters, tables, floors and walls; processing equipment such as tanks,vats, lines, pumps and hoses (e.g., dairy processing equipment forprocessing milk, cheese, ice cream and other dairy products); andtransportation vehicles. Containers include glass bottles, PVC orpolyolefin film sacks, cans, polyester, PEN or PET bottles of variousvolumes (100 ml to 2 liter, etc.), one gallon milk containers, paperboard juice or milk containers, etc.

The antimicrobial compositions can also be used on or in otherindustrial equipment and in other industrial process streams such asheaters, cooling towers, boilers, retort waters, rinse waters, asepticpackaging wash waters, and the like. The compositions can be used totreat microbes and odors in recreational waters such as in pools, spas,recreational flumes and water slides, fountains, and the like.

A filter containing the composition can reduce the population ofmicroorganisms in air and liquids. Such a filter can remove water andair-born pathogens such as Legionella.

The present compositions can be employed for reducing the population ofmicrobes, fruit flies, or other insect larva on a drain or othersurface.

The composition may also be employed by dipping food processingequipment into the use solution, soaking the equipment for a timesufficient to sanitize the equipment, and wiping or draining excesssolution off the equipment, The composition may be further employed byspraying or wiping food processing surfaces with the use solution,keeping the surfaces wet for a time sufficient to sanitize the surfaces,and removing excess solution by wiping, draining vertically, vacuuming,etc.

The composition of the invention may also be used in a method ofsanitizing hard surfaces such as institutional type equipment, utensils,dishes, health care equipment or tools, and other hard surfaces. Thecomposition may also be employed in sanitizing clothing items or fabricwhich have become contaminated. The use solution is contacted with anyof the above contaminated surfaces or items at use temperatures in therange of about 4° C. to 60° C., for a period of time effective tosanitize, disinfect, or sterilize the surface or item.

The antimicrobial compositions can be applied to microbes or to soiledor cleaned surfaces using a variety of methods. These methods canoperate on an object, surface, in a body or stream of water or a gas, orthe like, by contacting the object, surface, body, or stream with acomposition of the invention. Contacting can include any of numerousmethods for applying a composition, such as spraying the composition,immersing the object in the composition, foam or gel treating the objectwith the composition, or a combination thereof.

A concentrate or use concentration of a composition of the presentinvention can be applied to or brought into contact with an object byany conventional method or apparatus for applying an antimicrobial orcleaning composition to an object. For example, the object can be wipedwith, sprayed with, foamed on, and/or immersed in the composition, or ause solution made from the composition. The composition can be sprayed,foamed, or wiped onto a surface; the composition can be caused to flowover the surface, or the surface can be dipped into the composition.Contacting can be manual or by machine. Food processing surfaces, foodproducts, food processing or transport waters, and the like can betreated with liquid, foam, gel, aerosol, gas, wax, solid, or powderedstabilized compositions according to the invention, or solutionscontaining these compositions.

The present invention may be better understood with reference to thefollowing examples. These examples are intended to be representative ofspecific embodiments of the invention, and are not intended as limitingthe scope of the invention.

EXAMPLES

Compositions According to the Present Invention wt-% Ingredient A B C DE F peroxyacetic acid 0.14 0.12 0.065 0.060 0.055  0.035 peroxyoctanoicacid 0.07 0.07 0.05 δ⁴ δ δ glacial acetic acid 4 3 3 2 1.8 0.5 octanoicacid 0.2 0.2 0.15 0.15 0.1 0.1 hydrogen peroxide 5 5 3.5 3.2 3.2 1.8benzotriazole 0.25 0.25 0.25 0.1 0.06 0.1 sodium acetate 1 0.75 0.5 0.250.15 0.1 sequestrant¹ 2 0.75 0.5 0.25 0.1 2.5 hydrotrope² 5 2.5 0.5 0.250.1 0.1 nonionic surfactant³ 4 4 1.5 1.5 0.35 0.3 fragrance 0.3 0.3 0.20.1 0.1 0.1 ¹HEDP sold under the tradename DEQUEST ®2010 ²adipropyleneglycol n-butyl ether sold under the tradename DOWANOL ® DPnB³a mixture of nonionic surfactants sold under the tradenames SURFONIC ®L24-17 and SURFONIC ® 24-7 ⁴δ Indicates that the amount ofperoxyoctanoic acid was less than the limit of detection, 0.0004 wt-%.However, peroxyoctanoic acid is in equilibrium with octanoic acid andhydrogen peroxide and it should be present.

The balance of each of compositions A-F was water and each was at a pHof about 3.

Example 1 Storage Stability

This experiment demonstrates that embodiments of the present compositioncan have long shelf life, for example, a minimum shelf life of 1 year.For example, the antimicrobial components of the test composition Eremain stable during accelerated storage stability experiments.

Materials and Methods

Hydrogen peroxide content was determined by an oxidation-reductiontitration with potassium permanganate in an acidified water dilution ofthe sample. After the endpoint of this titration was reached, an excessof potassium iodide was added to the solution to measure concentrationof peroxyacid. Potassium iodide reacted with peroxyacid to liberateiodine which was titrated with a standard solution of sodiumthiosulfate.

Octanoic acid content is determined by reverse-phase high pressureliquid chromatography, refractive index detection and comparison of peakareas to an external standard. A Waters 4.6 mm/250 mm PN#WATO 54275reverse-phase column was employed with an acetonitrile/acetic acidmobile phase.

Results

Table 1A shows the stability composition E when held for 5 weeks at 40°C. within a standard container. One month of stability at 40° C. isgenerally a good measure of stability for one year shelf life undertypical conditions. It is desirable for the concentration ofperoxyacetic acid to remain above 425 ppm after one month at 40° C. Itis desirable for the concentration of octanoic acid to remain above 900ppm after one month at 40° C. It is desirable for the concentration ofhydrogen peroxide to remain above 2.85 wt-% after one month at 40° C.

TABLE 1A 40° C. Accelerated Storage Stability Time Peroxyacetic OctanoicH₂O₂ (Weeks) Acid (ppm) Acid (wt-%) (wt-%) Sample 1 0 600 0.095 3.2 2530 0.094 3.2 4 560 0.097 3.2 5 580 0.096 3.2 Sample 2 0 590 0.094 3.3 2530 0.094 3.2 4 560 0.097 3.2 5 590 0.097 3.2 Sample 3 0 580 0.094 3.2 2520 0.094 3.2 4 570 0.095 3.2 5 580 0.096 3.2 Sample 4 0 560 0.094 3.1 2520 0.094 3.2 4 570 0.098 3.2 5 590 0.098 3.2 Sample 5 0 560 0.092 3.2 2520 0.095 3.3 4 580 0.097 3.2 5 610 0.096 3.3

Table 1B shows the stability of active antimicrobial components incomposition RTU E of Table B when held for 13 months at ambient roomtemperatures (about 20° C. to about 25° C.) in a standard container.This testing confirms a minimum composition shelf life of biocidalefficacy and chemical stability of 1 year.

TABLE 1B Long Term Ambient Temperature Storage Stability TimePeroxyacetic Octanoic H₂O₂ (Months) Acid (ppm) Acid (wt-%) (wt-%) Sample1 0 600 0.095 3.2 5 560 0.096 3.3 6 530 0.103 3.3 9 540 0.092 3.3 12 5300.104 3.2 13 530 0.093 3.3 Sample 2 0 590 0.094 3.3 5 560 0.097 3.3 6520 0.102 3.3 9 540 0.096 3.3 12 510 0.098 3.3 13 530 0.098 3.3 Sample 30 580 0.094 3.2 5 560 0.097 3.2 6 530 0.101 3.4 9 560 0.096 3.3 12 5300.098 3.3 13 540 0.097 3.3 Sample 4 0 560 0.094 3.1 5 550 0.097 3.2 6530 0.096 3.3 9 560 0.091 3.3 12 520 0.096 3.3 13 530 0.098 3.3 Sample 50 560 0.092 3.2 5 550 0.098 3.3 6 540 0.098 3.3 9 560 0.090 3.3 12 5300.097 3.3 13 540 0.093 3.2

Conclusion

Tables 1A and 1B show the activity of hydrogen peroxide, peroxyaceticacid and octanoic acid do not appreciably change in these stabilitystudies. The stability of the RTU E antimicrobial components confirms aminimum biocidal efficacy and chemical stability of 1 year.

Example 2 Hospital Disinfection Efficacy

This experiment demonstrates that compositions of the present inventionhave antimicrobial activity that meets and exceeds the standards ofefficacy for hospital disinfection.

Materials and Methods

Testing was conducted following the Association of Official AnalyticalChemists (hereafter AOAC) Use-Dilution Method 955.14, 955.15 and 964.02,Official Methods of Analysis of the AOAC International, 15^(th) edition,2005. Testing was conducted at 425 ppm peroxyacetic acid. A compositionwas considered to have adequate antimicrobial activity when there was nogrowth in 59 of 60 tubes.

Composition E was tested. This composition was prepared to include 3.2wt. % hydrogen peroxide, 1.8 wt-% glacial acetic acid, 1000 ppm octanoicacid, and about 500 ppm total peroxyacids.

Results

Table 2 shows antimicrobial activity of composition E that meets thestandards of efficacy for hospital disinfection.

TABLE 2 Hospital Disinfection Antibacterial Efficacy ATCC CFU/TubeMicrobe Free Microbe Accession No. (ave.) Tubes S. choleraesuis 6538 2.8× 10⁶ 60/60 (4 minutes) S. aureus 10708 1.3 × 10⁷ 60/60 (4 minutes) P.aeruginosa 15442 2.5 × 10⁷ 60/60 (4 minutes)

Conclusion

Table 2 demonstrates that a composition of the present invention hasantimicrobial activity that meets and exceeds the standards of efficacyfor hospital disinfection. It disinfected sixty out of sixty tubes in astandard analysis for antimicrobial efficiency against hospitalmicrobes.

Example 3 Disinfection Efficacy Against Additional Organisms

This experiment demonstrates that compositions of the present inventionare effective against bacteria, such as those from healthcare and foodpreparation environments.

Materials and Methods

Testing was conducted as above but with only 10 stainless steel tube perorganism. A composition was considered to have adequate antimicrobialactivity when there was no growth in 10 of 10 tubes.

Results

Table 3 shows data for disinfection by composition E against additionalorganisms.

TABLE 3 Disinfection Efficacy Against Bacteria of Healthcare and FoodBorne Illness ATCC CFU/Tube Microbe Free Microbe Accession No. (ave.)Tubes Enterococcus 51299 2.3 × 10⁷ 10/10 facials - VRE* (4 minutes)Staphylococcus 33592 8.9 × 10⁵ 10/10 aureus - MRSA* (4 minutes)Escherichia coli 11229 1.0 × 10⁷ 10/10 (4 minutes) Escherichia coli43895 1.6 × 10⁷ 10/10 O157:H7 (4 minutes) Klebsiella 4352 5.4 × 10⁶10/10 pneumoniae (4 minutes) Shigella flexneri 9380 3.1 × 10⁷ 10/10 (4minutes) Proteus vulgaris 13315 1.5 × 10⁷ 10/10 (4 minutes)Enteroabacter 13048 1.6 × 10⁷ 10/10 aerogenes (4 minutes) Clostridiumdifficile 9689   2 × 10⁷ 10/10 (vegetative) (4 minutes)) StaphylococcusHIP 5836 1.12 × 10⁶  10/10 aureus - VISA* (4 minutes) *Antibioticresistant bacteria: VRE—Vancomycin Resistant Enterococcus faecalis;MRSA—Methicillin Resistant Staphylococcus aureus;VISA—Vancomycin-Intermediate/Resistant Staphylococcus aureus

Conclusion

The results in Table 3 demonstrate that a composition of the presentinvention was an effective disinfectant against numerous bacteria fromhealthcare and food borne illnesses. It disinfected ten out of ten tubesfor all microbes tested above.

Example 4 Fungicidal Efficacy

This experiment demonstrates that compositions according to the presentinvention have antifungal activity against pathogenic fungus, yeast, andmildew.

Materials and Methods

Testing was conducted as in Example 2 with the following modifications.Stainless steel penicillin carriers were inoculated with a soilsuspension at 1 mL per carrier and incubated. The soil suspension wasaspirated off and the carriers were aseptically transferred to sterilepetri dishes matted with filter paper. The petri dishes were covered anddried at 35° C. for 40 min. Following drying, the microorganism wasaseptically transferred to individual tubes containing 10 mL of the testsubstance. After the 4 minute exposure period, the carriers weresubsequently subcultured into individual tubes of the subculture medium.

Results

Table 4 shows data for fungicidal activity of composition E.

TABLE 4 Fungicidal Efficacy of the Present Compositions ATCC AccessionCFU/Tube Microbe Free Microbe No. (ave.) Tubes Pathogenic FungusTrichophyton 9533 1.4 × 10⁷ 60/60 mentagrophytes Conidia (Athletes'Foot) suspension (4 minutes) Yeast Candida albicans 10231 5.0 × 10⁶10/10 (5 minutes) Mildew Aspergillus niger 6275 8.8 × 10⁶ 60/60 (4minutes) Conidia suspension

Conclusion

Table 4 demonstrates that a composition of the present invention waseffective against common forms pathogenic fungus, yeast, and mildew. Itresulted in complete kill, as represented by complete kill in 60 out of60 tubes for each of pathogenic fungus, yeast, and mildew tested.

Example 5 Quantitative Tuberculocidal Efficacy

This experiment demonstrates that a composition according to the presentinvention has effective antimicrobial activity against Mycobacteriumbovis—BCG, a tuberculodical microbe.

Materials and Methods

Testing follows standard U.S. EPA protocol for a quantitativetuberculocidal test. An embodiment of the composition of the presentinvention was diluted with sterile deionized water at 425 ppm and testedagainst Mycobacterium bovis—BCG. A composition was considered to haveadequate antimicrobial activity when there was 5 log₁₀ reduction in thepopulation of mycobacteria.

Results

Table 5 shows results obtained from a 2.5 minute exposure of themycobacterium to composition E.

TABLE 5 Quantitative Tuberculocidal Efficacy Test Results CFU/Plate CFU/2.5 Minutes CFU/ CFU/ Log Tube 10⁻¹ 10⁻³ Plate mL Reduc- Microbe (ave.)Dilution Dilution (ave.) (ave.) tion Mycobacterium 6.8 × 10⁴ 0 0 0 <2 >5bovis 0 0 BCG 454C150 0 0 (2.5 minutes) 0 0 0 0 0 <2 >5 0 0 0 0 0 0 0 00 <2 >5

Conclusion

A composition of the present invention was effective againsttuberculocidals as measured by a standard U.S. EPA protocol. Itdemonstrated a greater than 5 log reduction of mycobacterium bovis inthe assay. There were no surviving organisms, complete kill wasachieved.

Example 6 Virucidal Efficacy

This experiment demonstrates that a composition of the present inventionhas effective virucidal activity against numerous common viruses.

Materials and Methods

Testing was conducted according to ASTM E1053-97. Briefly: The virussuspension was dried on an inanimate, nonporous surface. Theantimicrobial was added over the dried virus as a use dilution solutionor sprayed from an aerosol can or trigger spray container and exposed atthe appropriate temperature for the recommended time. The virus titer ofan untreated surface was determined by the median infective dose (ID₅₀)method of virus titration. Cytotoxicity to the host system of theantimicrobial at the tested concentration was determined by an LD⁵⁰method. The virus-antimicrobial mixture was assayed in numerous units ofthe host system at a dilution just beyond the cytotoxicity range of theantimicrobial. The extent of virus inactivation by the antimicrobial wasdetermined. Results are recorded as log₁₀-virus inactivated.

Results

Table 6 shows virucidal activity of composition E diluted to 425 ppmperoxyacetic acid.

TABLE 6 Virucidal Efficacy Test Results ATCC Accession CFU/Tube CFU/TubeMicrobe No. (ave.) (ave.) - post Log Reduction Feline Calicivirus VR-78210^(7.0)   10^(1.5) >5.47 log (Norwalk Complete Inactivation Surrogate)No Viable Virus (4 minutes) Human VR-740 10^(4.5) <10^(0.5) >4 logCoronavirus Complete Inactivation SARS (4 minutes) No Viable Virus HumanStrain 10^(5.75) <10^(1.5) >4 log Immunodeficiency HTLV-III_(B) Completeinactivation Virus (HIV) Type 1 No Viable Virus (30 seconds) RespiratoryVR-26 10^(5.5)   10^(1.5) >4 log Syncytial Virus Complete Inactivation(RSV) No Viable Virus (4 minutes) Avian Influenza A VR-2072, 10^(5.0)<10^(0.5) >4.5 log Serotype H5N3 Strain A Complete Inactivation (4minutes) No Viable Virus Adenovirus Type 4 VR-4 10^(5.5)   10^(1.5) >4log (4 minutes) Complete Inactivation No Viable Virus Rhinovirus Type 37VR-1147, 10^(5.25) <10^(0.5) >4.75 log (4 minutes) Strain 151-1 CompleteInactivation No Viable Virus Rotavirus Strain WA 10^(6.75)  10^(1.5) >5.25 log (4 minutes) Complete Inactivation No viable VirusHepatitis B Virus Duck 10^(5.0) <10^(1.5) >3.21 Hepatitis B CompleteInactivation Virus No Viable Virus

Conclusion

Composition E showed effective anti viral activity against nine commonviruses. There was no viable virus and complete inactivation afterexposure to composition E for four minutes.

Example 7 A Composition of the Present Invention Kills Spores Fast atRoom Temperature

This experiment demonstrates that a composition according to the presentinvention showed fast and effective sporicidal activity against sporesof three spore forming pathogens when tested at room temperature.

Materials and Methods

Testing was conducted following AOAC Official Method 966.04, SporicidalActivity of Disinfectants. Testing was conducted at using a compositionaccording to the present invention at 425 ppm peroxyacetic acid.Sporicidal activity was measured at 20° C. A composition was consideredto have adequate antimicrobial activity when there was no growth in 60of 60 tubes.

Results

Table 7 shows results obtained for sporicidal activity of composition E.

TABLE 7 Sporicidal (Cold Sterilant Test) Efficacy Test Results ATCCAccession CFU/Tube Microbe Free Microbe No. (ave.) Tubes Bacillussubtilis - 19659 3.0 × 10⁴ 60/60 Porcelain Carriers (30 minutes)Bacillus subtilis - 19659 5.4 × 10⁴ 60/60 Sutures (30 minutes)Clostridium sporogenes - 3584 5.3 × 10⁴ 60/60 Porcelain Carriers (30minutes) Clostridium sporogenes - 3584 1.8 × 10⁶ 60/60 Sutures (30minutes) Clostridium difficile - 9689 6.8 × 10⁴ 60/60 Porcelain Carriers(20 minutes) Clostridium difficile - 9689 1.1 × 10⁴ 60/60 Sutures (20minutes)

TABLE 8 Comparison of Sporicidal Activity With Commercial Products TimeRequired Composition for Effective (Active Ingredient(s)) SporicidalAction¹ Inventive Composition E 30 minutes at 25° C. (3.15% hydrogenperoxide, 424 ppm peroxyacetic acid, 950 ppm octanoic acid) CommercialProduct A 32 hours at 50° C.² (5.75% ortho-phthaldehyde (OPA))Commercial Product B 12 hours at 25° C. (1.12% Glutaraldehyde and 1.93%phenol/phenate) Commercial Product C 24 hours at 25° C. (hypochloriteand hypochlorous acid, 650-675 ppm active free chlorine CommercialProduct D  5 hours at 25° C. (8.3% Hydrogen Peroxide and 7.0%Peroxyacetic Acid) Commercial Product E  6 hours at 20° C. (7.5%Hydrogen Peroxide) ¹Results reported for commercial products areprovided by each manufacturer for testing in AOAC Sporicidal ActivityTest or a modified version of that test. Center for Devices andRadiological Health, Office of Device Evaluation, U.S. Food and DrugAdministration, http://www.fda.gov/cdrh/ode/germlab.html ²Tested as usesolution containing 0.05% OPA

Conclusion

Composition E demonstrated effective sporicidal activity against sixcommon microbes. Sixty out of sixty tubes were microbe free after nomore than thirty minutes incubation with composition E. Composition Ekills spores in 1/10^(th) to 1/64^(th) the amount of time of severalcommercial products.

Example 8 A Composition of the Present Invention Kills B. cereus Sporesin a Test for Aseptic Packaging of Foods

This experiment demonstrates that a composition according to the presentinvention showed fast and effective sporicidal activity against sporesof B. cereus when tested for suitability in aseptic packaging for foods.

Materials and Methods

Sporicidal activity was measured against spores of Bacillus cereus ATCCwith a 19 second exposure time at 60° C. using composition E at 490 ppmperoxyacetic acid. A composition was considered to have adequateantimicrobial activity when there was no growth in 30 of 30 tubes.

Results

In each of two tests, composition E killed the B. cereus spores in 30 of30 stainless steel tubes.

Conclusion

Composition E demonstrated effective sporicidal activity against B.cereus spores. Thirty out of thirty tubes were microbe free after nomore than 19 sec exposure to composition E.

Example 9 A Composition of the Present Invention is of Low Toxicity

This example demonstrates that a composition of the present inventionshowed no or little adverse reaction in standard texts of toxicity.

Materials and Methods

Toxicity testing was performed according to EPA Health Effects TestGuidelines, OPPTS 870.1000, Acute Toxicity Testing, December 2002.Testing was performed with composition E at a concentration of 3.2%-3.3wt-% hydrogen peroxide, 450-550 ppm peroxyacetic acid, 950-1000 ppmoctanoic acid, and <4 ppm peroxyoctanoic acid.

Results

In a test of toxicity from acute inhalation, composition E had an LC₅₀of >2.31 mg/L. Composition E had an LD₅₀ of >5000 mg/kg in a test oftoxicity from acute oral administration. In a test of toxicity fromacute dermal contact, composition E had an LD₅₀ of >5000 mg/kg. Thiscomposition tested as only a slight irritant in a test for primary skinirritation. Each of these tests place it in category IV, the lowestlevel of toxicity, in the EPA standards. The composition is not acontact sensitizer in a test of dermal sensitization. The compositioncaused some eye irritation.

Example 10 Low Corrosion by the Present Compositions

This experiment demonstrates that a composition of the present inventionshowed a low corrosion rate as measured on brass CDA 360.

Materials and Methods

Corrosion testing was performed according to ASTM G1-90 and G31-72.Compositions of the invention were tested for corrosion of coupons ofbrass CDA 360. The testing included weighting a clean, dry metal coupon,immersing the coupon in the test composition for 8 hours at 50° C. Thecoupons are then removed, dried, and weighed again. The weight loss isconverted to thickness loss based on the surface area and density of thecoupon. The measurements are compared to a water control. Compositionstested include peroxycarboxylic acid compositions and with and withouthexanoic acid and/or benzotriazole or heptanoic acid and/orbenzotriazole.

Results

Table 9 and FIG. 1 show results obtained for testing corrosion of brassby composition E and control compositions. The results show that acomposition containing a medium chain carboxylic acid (e.g., hexanoicacid, heptanoic acid, octanoic acid, or nonanoic acid) and a triazolecorrosion inhibitor provides a greater decrease in corrosion than wouldbe expected by comparison to compositions including only the carboxylicacid or only the triazole corrosion inhibitor. Compositions K, N, and Pcorroded brass to only less than 100 mil/year (i.e., 57 mil, 69 mil, and87 mil, respectively). Interestingly, compositions including mandelicacid, adipic acid, and a mixture of adipic, glutaric and succinic acidsdid not exhibit reduced corrosion. The compositions were at pH 3.

Compositions G-N were determined to be stable when held for one month at40° C. within a typical commercial-type container according to thestandards described above in Example 1.

TABLE 9 Brass CDA 360 Corrosion Results wt-% G H I J K L M N O P Q RGlacial Acetic Acid 1.75 1.75 1.75 1.74 1.75 1.75 1.75 1.75 1.76 1.761.76 1.76 Sequestrant 0.10 0.10 0.12 0.12 0.10 0.10 0.10 0.10 0.10 0.100.10 0.10 Hydrogen Peroxide, 35% 9.00 9.00 8.98 8.98 9.00 9.00 9.00 9.019.08 9.08 9.08 9.07 Nonionic surfactant 0.30 0.30 0.30 0.30 0.30 0.300.43 0.43 0.30 0.30 0.30 0.30 Nonionic surfactant 0.05 0.05 0.05 0.050.05 0.05 0.05 0.06 0.05 0.05 0.05 0.06 Sodium Acetate 0.14 0.13 0.150.15 0.13 0.14 0.14 0.13 0.16 0.13 0.13 0.13 Solvent 0.10 0.10 0.10 0.100.10 0.10 0.10 0.10 0.11 0.10 0.10 0.10 Fragrance 0.10 0.10 0.10 0.100.10 0.10 0.10 0.10 0.10 0.11 0.11 0.11 Hexanoic Acid 0.10 0.10 — — — —— — — — — — Heptanoic Acid — — 0.10 0.10 — — — — — — — — Octanoic Acid —— — — 0.10 0.10 — — — — — — Nonanoic Acid — — — — — — 0.10 0.10 — — — —Mandelic Acid — — — — — — — — 0.10 — — — Salicylic Acid — — — — — — — —— 0.10 — — Adipic Acid — — — — — — — — — — 0.10 — Adipic, Glutaric, and— — — — — — — — — — — 0.10 Succinic Acids* Benzotriazole — 0.06 — 0.070.06 — — 0.06 0.06 0.06 0.06 0.06 Deionized Water 88.36 88.31 88.3588.29 88.31 88.36 88.23 88.15 88.17 88.20 88.20 88.20 Trial 1 Corrosion(mpy)** 689 100 673 53 57 780 784 69 753 87 705 684 Trial 2 Corrosion(mpy) 693 112 685 55 — 786 790 70 *mixture of these acids sold under thetradename Sokolan DCS **mpy—mils per year (mil = 0.001 inch)

Conclusion

Compositions according to the present invention and including a mediumchain mono carboxylic acid (e.g., hexanoic acid, heptanoic acid,octanoic acid, and nonanoic acid) or a benzoic acid derivative (e.g.,benzoic acid and salicylic acid) and a triazole corrosion inhibitorcaused a significantly lower corrosion rate as measured on brass CDA 360when compared to compositions including only the carboxylic acid or thecorrosion inhibitor.

Example 11 Cleaning Performance

This experiment demonstrates that a composition of the present inventionwas an effective detergent as measured by the ability to remove soil.Bacteria, fungi or viruses held within the soil are treated moreeffectively when an antimicrobial component is mixed with a detergentcomponent.

Materials and Methods

Three different soils were used for testing. A fatty food soil includingfat, oil, and an iron compound was representative of residual food soilstypically found on kitchen, food process, food preparation, food servingenvironmental surfaces and the like. A black oily soil largely includingpetroleum distillate, oil, and earth was representative of waterinsoluble greasy/oily soils, such as those carried onto surfaces fromthe general environment, cosmetics, equipment, instruments, tools,devices and the like. An inorganic bathtub/shower soil includingminerals, soapy residue, and synthetic dead skin cells representedinorganic hard water deposits and soap scum found on typical bathroomand sink area surfaces. Tests using the fatty food soil and black foodsoil were generally performed according to ASTM D 4488-95. Tests usingthe Inorganic Bathtub/Shower Soil were generally performed according toASTM D 5343-97.

Results

Table 10 shows the cleaning results obtained for composition E of thepresent invention against the fatty food soil, the black oily soil, andthe inorganic bathtub/shower soil. Cleaning performance against eachsoil was measured by wt-% removal of the soil from the surface beingcleaned.

TABLE 10 Soil Cleaning Performance Results Summary Soil Soil Removal(wt-%) Fatty Food Soil 87 Black Oily Soil 51 Inorganic Bathtub/ShowerSoil 62

Conclusion

Composition E of the present invention demonstrated effective detergentaction against three common types of soil that an antimicrobialcomposition would be used on. The detergent removed and suspended soilso that the antimicrobial component can destroy the bacteria, fungi orviruses held within the soil and upon the surface being treated.

Example 12 Glass Cleaning Performance

This experiment demonstrated that a composition of the present inventionwas an effective glass cleaner.

Procedure

Composition E was tested for glass cleaning performance according toCSMA Detergents Division Test Method Designation DCC-09 (3^(rd) ed.,1995) with the following test soil modification: 1% beef suet in hexane.Soil application, cleaning and rating follow the DCC-09 protocol.Results were graded by visual ranking on a scale of 1 to 4 for cleaning(soil removal), streaking, and smearing. A rating of 4 is best and arating of 1 is poorest result.

Results

Table 11 shows that composition E scores consistently better than fourcommon commercial products in all three categories tested.

TABLE 11 Glass Cleaning Performance Results Cleaning Streaking SmearingAverage Standard Average Standard Average Standard Composition Rating1-4 Deviation Rating 1-4 Deviation Rating 1-4 Deviation CommercialProduct 1 1.8 0.4 1.0 0.0 2.6 0.7 Commercial Product 2 2.3 0.5 2.0 0.92.8 0.4 Commercial Product 3 1.9 0.5 1.4 0.5 2.5 0.5 Commercial Product4 2.2 0.8 1.8 1.0 2.3 0.8 Composition E 3.2 0.3 2.8 0.3 2.9 0.1Cleaning, Streaking, and Smearing Rating Protocol** Cleaning: Streaking:Smearing: 4 = Total soil removal 4 = None 4 = None 3 = Good soil removal3 = Slight streaking 3 = Slight smear 2 = Moderate soil removal 2 =Moderate streaking 2 = Moderate smear 1 = Poor soil removal 1 = Severestreaking 1 = Severe smear *All products were prediluted and ready-to-use **Average of 2 tests, 3 individual graders

Conclusion

Composition E showed better glass cleaning performance than the fourcommon commercial products it was tested against. It had an averagehigher score and a lower standard deviation for all three categorieswithin the glass cleaning test.

Example 13 Additional Compositions According to the Present Invention

Additional compositions according to the present invention were assessedfor their stability in an accelerated test and were demonstrated to bestable for the equivalent of 1 year at ambient conditions.

Materials and Methods

Stability was measured generally as described as in Example 1 for thecompositions listed on Table 12 below.

TABLE 12 Additional Compositions According to the Present Invention wt-%Ingredient E-1 S T U V W X Y glacial acetic 1.7 1.8 1.8 1.8 1.8 1.5 1.71.8 acid octanoic acid 0.11 0.10 — 0.10 0.11 0.10 0.11 0.10 hydrogen 9.09.0 9.0 9.0 7.7 9.0 9.0 9.0 peroxide (35%) benzotriazole 0.06 0.08 —0.06 0.06 0.05 0.06 0.06 sodium acetate 0.19 0.16 0.16 0.14 0.14 0.190.16 0.17 sequestrant¹ 0.09 0.11 0.11 — 0.11 0.11 0.13 0.13 hydrotrope²0.11 0.10 0.10 0.10 0.11 0.12 0.10 0.10 first nonionic 0.32 — — 0.380.32 0.31 — — surfactant ³ second 0.05 0.04 0.05 0.05 0.06 0.06 0.050.05 nonionic surfactant ⁴ third nonionic — — — — — — 0.21 — surfactant⁵lauryl amine — — — — — — — 1.00 oxide (30%) fragrance 0.10 0.10 — 0.110.09 0.10 0.10 0.10 pH 3.3 3.1 3.0 3.3 3.0 3.2 3.1 3.3 ¹HEDP sold underthe tradename DEQUEST ®2010, percent listed is the commercial productwhich is 60% HEDP. ²a dipropyleneglycol n-butyl ether sold under thetradename DOWANOL ® DPnB. ³ linear alcohol (c12-c14) 17 mole ethoxylatesold under the tradename SURFONIC ® L24-17. ⁴ linear alcohol c12-c14 7mole ethoxylate sold under the tradename SURFONIC ® 24-7. ⁵eo/po blockcopolymer with avg m.w. 14,600 sold under the tradename PLURONIC F108.The balance of each of compositions E-1 and S-Y was water. The amountsof ingredients are the amounts of raw materials added before theperoxycarboxylic acid was formed.

Results

Results of the stability testing of compositions E-1 and S-X are listedTable 13 below.

TABLE 13 Stability of Compositions E-1 and S-Y Days SinceComposition/ppm peroxycarboxylic acid Formulation E-1 S T U V W X Y 0495 659 718 161 631 499 697 121 33 459 480 540 261 438 446 526

In each composition, the amount of peroxycarboxylic acid at 33 days wasgreater than or equal to 425 ppm. These compositions are stablecompositions according to the present invention.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes a mixture oftwo or more compounds. It should also be noted that the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains.

The invention has been described with reference to various specific andpreferred embodiments and techniques. However, it should be understoodthat many variations and modifications may be made while remainingwithin the spirit and scope of the invention.

1. A shelf stable, ready to use peroxycarboxylic acid composition comprising: about 0.0001 to about 0.2 wt-% short chain peroxycarboxylic acid; about 1 to about 5 wt-% hydrogen peroxide; about 0.01 to about 5 wt-% short chain carboxylic acid; about 0.01 wt-% to about 5 wt-% nonionic surfactant; and about 0.01 wt-% to about 3 wt-% sequestrant; wherein: the composition is free of added mineral acid; the pH of the composition is about 1 to about 4; the ratio of hydrogen peroxide:peroxycarboxylic acid is about 30:1 to about 60:1; the composition is stable such that greater than 85% of the initial concentration of peroxycarboxylic acid remains after 1 year of storage at room temperature; and the ratio of hydrogen peroxide:protonated carboxylic acid is about 1:1 to about 2:1.
 2. The composition of claim 1, comprising: about 0.005 to about 0.2 wt-% short chain peroxycarboxylic acid; and about 0.5 to about 5 wt-% short chain carboxylic acid.
 3. The composition of claim 1, further comprising: about 0.0001 to about 0.004 wt-% medium chain peroxycarboxylic acid; and about 0.01 to about 0.3 wt-% medium chain carboxylic acid.
 4. The composition of claim 1, further comprising buffer, hydrotrope, corrosion inhibitor, or combination thereof.
 5. The composition of claim 4, comprising about 0.01 to about 2 wt-% buffer, the buffer comprising phosphate salt, citrate salt, formate salt, malate salt, or acetate salt.
 6. The composition of claim 4, comprising about 0.01 to about 2 wt-% buffer, the buffer being an acetate salt.
 7. The composition of claim 4, comprising about 0.01 to about 0.25 wt-% corrosion inhibitor.
 8. The composition of claim 7, wherein the corrosion inhibitor comprises a triazole corrosion inhibitor.
 9. The composition of claim 8, wherein the corrosion inhibitor comprises benzotriazole.
 10. The composition of claim 1, wherein the composition is ready to use with a concentration of from about 0.005 wt-% to about 0.2 wt-% of a peroxycarboxylic acid within about 2 to about 4 hours and wherein the composition is sufficiently stable that greater than 85% of the initial concentration of peroxycarboxylic remains after 1 year of storage at room temperature and ambient humidity.
 11. The composition of claim 1, further comprising about 0.01 to about 1 wt-% masking agent, the masking agent being chemically stable the composition for at least about 6 months at room temperature
 12. A low corrosion peroxycarboxylic acid composition comprising: about 0.0001 to about 0.2 wt-% peroxycarboxylic acid; about 1 to about 5 wt-% hydrogen peroxide; about 0.01 to about 5 wt-% medium chain mono carboxylic acid or benzoic acid derivative; about 0.01 to about 2 wt-% buffer; about 0.01 wt-% to about 5 wt-% nonionic surfactant; and about 0.01 wt-% to about 3 wt-% sequestrant; wherein: the composition is ready to use with a concentration of from about 0.005 wt-% to about 0.2 wt-% of the peroxycarboxylic acid within about 2 to about 4 hours; wherein the composition is stable such that greater than 85% of the initial concentration of peroxycarbonic acid remains after 1 year of storage at room temperature; the composition is free of added mineral acid; the pH of the composition is about 1 to about
 4. 13. The composition of claim 12, further comprising a corrosion inhibitor comprising a triazole corrosion inhibitor.
 14. The composition of claim 13, wherein the corrosion inhibitor comprises benzotriazole.
 15. The composition of claim 12, comprising about 0.01 to about 2 wt-% buffer, the buffer comprising phosphate salt, citrate salt, formate salt, malate salt, or acetate salt.
 16. The composition of claim 12, comprising about 0.01 to about 2 wt-% buffer, the buffer being an acetate salt.
 17. The composition of claim 12, comprising: about 0.005 to about 0.2 wt-% short chain peroxycarboxylic acid; and about 0.5 to about 5 wt-% short chain carboxylic acid.
 18. The composition of claim 12, comprising: about 0.0001 to about 0.004 wt-% medium chain peroxycarboxylic acid; and about 0.01 to about 0.3 wt-% medium chain carboxylic acid.
 19. The composition of claim 12, further comprising a hydrotrope.
 20. The composition of claim 12, wherein: the ratio of hydrogen peroxide:peroxycarboxylic acid is about 30:1 to about 60:1; and the ratio of hydrogen peroxide:protonated carboxylic acid is about 1:1 to about 2:1.
 21. The composition of claim 12, wherein the composition causes less than 200 mil per year corrosion of brass when evaluated according to ASTM G1-90 or ASTM G31-72.
 22. The composition of claim 12, further comprising about 0.01 to about 1 wt-% masking agent, the masking agent being chemically stable the composition for at least about 6 months at room temperature
 23. A method of reducing the population of bacterial endospores, comprising: contacting bacterial endospores with a composition comprising: about 0.0001 to about 0.2 wt-% short chain peroxycarboxylic acid; about 1 to about 5 wt-% hydrogen peroxide; about 0.01 to about 5 wt-% short chain carboxylic acid; about 0.01 wt-% to about 5 wt-% nonionic surfactant; and about 0.01 wt-% to about 3 wt-% sequestrant; wherein the composition is free of added mineral acid; the pH of the composition is about 1 to about 4; the ratio of hydrogen peroxide:peroxycarboxylic acid is about 30:1 to about 60:1; and the ratio of hydrogen peroxide:protonated carboxylic acid is about 1:1 to about 2:1; and achieving greater than 5 log reduction in the population of bacterial endospores in less than 1 hour under ambient conditions. 